TW202209351A - Bonding composition and formulation method for bonding composition - Google Patents
Bonding composition and formulation method for bonding composition Download PDFInfo
- Publication number
- TW202209351A TW202209351A TW110124644A TW110124644A TW202209351A TW 202209351 A TW202209351 A TW 202209351A TW 110124644 A TW110124644 A TW 110124644A TW 110124644 A TW110124644 A TW 110124644A TW 202209351 A TW202209351 A TW 202209351A
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- Prior art keywords
- metal
- bonding
- metal particles
- amine
- composition
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- 150000002940 palladium Chemical class 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- MJRKFYKONYYOJX-UHFFFAOYSA-J phosphonato phosphate;tin(4+) Chemical compound [Sn+4].[O-]P([O-])(=O)OP([O-])([O-])=O MJRKFYKONYYOJX-UHFFFAOYSA-J 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
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- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- FTNNQMMAOFBTNJ-UHFFFAOYSA-M silver;formate Chemical compound [Ag+].[O-]C=O FTNNQMMAOFBTNJ-UHFFFAOYSA-M 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
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- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Computer Hardware Design (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Conductive Materials (AREA)
Abstract
Description
本發明是有關於一種含有金屬粒子的接合用組成物及接合用組成物的製備方法。The present invention relates to a bonding composition containing metal particles and a method for producing the bonding composition.
先前,為了將金屬零件與金屬零件機械性、電性及/或熱性接合而使用接合材料。作為所述接合材料,例如可列舉:焊料、導電性接著劑、銀糊、各向異性導電性膜等。該些接合材料不僅於金屬零件彼此的接合中使用,而且有時亦於金屬零件、與陶瓷零件、樹脂零件等的接合中使用。例如,近年來有時於將發光二極體(light emitting diode,LED)等發光元件、半導體晶片等接合於基板的用途、或將該些基板進而接合於放熱構件的用途中使用接合材料。Conventionally, bonding materials have been used for mechanically, electrically and/or thermally bonding metal parts to metal parts. As said joining material, a solder, a conductive adhesive, a silver paste, an anisotropic conductive film, etc. are mentioned, for example. These joining materials are used not only for joining metal parts to each other, but also for joining metal parts, ceramic parts, resin parts, and the like in some cases. For example, in recent years, bonding materials are sometimes used for bonding light-emitting elements such as light emitting diodes (LEDs), semiconductor wafers, and the like to substrates, or for bonding these substrates to heat radiating members.
包括LED等發光元件的高亮度的照明器件或發光器件、被稱為功率器件的包括在高溫下進行高效率的動作的半導體元件的半導體器件等存在器件使用時的驅動溫度高的傾向。焊料的熔點比該些器件的驅動溫度低,因此並不適於LED等發光元件、半導體晶片等的接合。進而,近年來就環境保護或「與電氣電子設備中所含的特定有害物質的使用限制相關的歐洲議會及理事會指令」(危害性物質限制指令(Restriction of Hazardous Substances,RoHS))的規定的觀點而言,要求不包含鉛的接合材料。High-brightness lighting devices or light-emitting devices including light-emitting elements such as LEDs, and semiconductor devices including semiconductor elements that operate efficiently at high temperatures, such as power devices, tend to have high drive temperatures during device use. The melting point of the solder is lower than the driving temperature of these devices, so it is not suitable for bonding of light-emitting elements such as LEDs, semiconductor wafers, and the like. Furthermore, in recent years, regulations concerning environmental protection or the "European Parliament and Council Directive on the Restriction of the Use of Specified Hazardous Substances Contained in Electrical and Electronic Equipment" (Restriction of Hazardous Substances (RoHS)) From a viewpoint, a bonding material that does not contain lead is required.
作為耐熱性高、且不含有鉛的新的接合材料,研究有含有金屬奈米粒子的接合用組成物(例如,參照專利文獻1~專利文獻3等)。As a new bonding material having high heat resistance and containing no lead, a bonding composition containing metal nanoparticles has been studied (for example, refer to Patent Documents 1 to 3, etc.).
專利文獻1中揭示有使用銀奈米粒子作為接合材料並進行低溫燒結(80℃~120℃)的技術,且揭示有如下的接合材料,其包含由碳數6以下的有機物被覆且平均一次粒徑為10 nm~30 nm的奈米銀粒子、由碳數6以下的有機物被覆且平均一次粒徑為100 nm~200 nm的奈米銀粒子、以及作為分散劑的沸點不同的兩種溶媒。而且記載如下內容:減輕於預乾燥步驟的脫溶媒過程的接合層的面內引起的中央與端部的乾燥不均的產生,提高接合後的耐熱衝擊性。Patent Document 1 discloses a technique of using silver nanoparticles as a bonding material and performing low-temperature sintering (80° C. to 120° C.), and discloses a bonding material comprising an average primary particle coated with an organic substance having a carbon number of 6 or less Nano-silver particles with a diameter of 10 nm to 30 nm, nano-silver particles coated with an organic substance having a carbon number of 6 or less and an average primary particle size of 100 nm to 200 nm, and two solvents with different boiling points as dispersants. In addition, it is described that the occurrence of drying unevenness between the center and edge portions in the surface of the bonding layer in the desolvation process of the pre-drying step is reduced, and the thermal shock resistance after bonding is improved.
專利文獻2中揭示有如下的接合材料,其包含混合了銀微粒子與溶劑的銀糊,所述接合材料中溶劑為二醇,且混合有作為添加劑的三醇與作為燒結促進劑的二羧酸。而且,記載如下內容:可防止預乾燥膜的裂紋或剝離,並且經由預乾燥膜的突起部亦可將非接合物彼此良好地接合。Patent Document 2 discloses a bonding material comprising a silver paste in which fine silver particles and a solvent are mixed, in which the solvent is a diol, and a triol as an additive and a dicarboxylic acid as a sintering accelerator are mixed . Further, it is described that cracks and peeling of the pre-dried film can be prevented, and non-bonded objects can be well joined to each other via the protrusions of the pre-dried film.
專利文獻3中以提供即便於比較低的溫度下亦可不加壓地進行接合、且可獲得優異的接合強度的接合用組成物為目的,揭示一種接合材料,其為含有平均粒徑為20 nm~100 nm的第一金屬粒子、與分散介質的接合用組成物,所述分散介質相對於所述接合用組成物整體的含量為1.0重量%以上且未滿5.0重量%。 [現有技術文獻] [專利文獻]Patent Document 3 discloses a bonding material containing a bonding material having an average particle diameter of 20 nm for the purpose of providing a bonding composition that can be bonded without pressure even at a relatively low temperature and can obtain excellent bonding strength. A composition for bonding of a first metal particle having a thickness of ∼100 nm, and a dispersion medium in which the content of the dispersion medium relative to the entire composition for bonding is 1.0 wt % or more and less than 5.0 wt %. [Prior Art Literature] [Patent Literature]
專利文獻1:國際公開第2013/108408號 專利文獻2:日本專利特開2017-101264號公報 專利文獻3:國際公開第2019/142633號Patent Document 1: International Publication No. 2013/108408 Patent Document 2: Japanese Patent Laid-Open No. 2017-101264 Patent Document 3: International Publication No. 2019/142633
[發明所欲解決之課題] 如此,先前揭示有於使用金屬奈米粒子的接合中,可在比較低的溫度(未滿300℃)的煆燒溫度下進行燒結的接合材料。[The problem to be solved by the invention] In this way, a bonding material that can be sintered at a relatively low sintering temperature (less than 300° C.) in bonding using metal nanoparticles has been disclosed.
進而,近年來對包括LED等發光元件、半導體晶片等的器件有提高輸出的要求,且有時進行高積體化、或增大投入電力。因此,該些器件的驅動溫度進一步變高,存在接合材料的使用環境變得更嚴酷的傾向,因此對LED等發光元件、半導體晶片等的接合要求高的接合強度。另外,即便為具有高的接合強度的接合材料,若塗佈穩定性差,則亦有發生周邊構件的電性短路、污染等的可能性,因此要求一種塗佈穩定性優異的接合材料。所述專利文獻1~專利文獻3中揭示有含有銀奈米粒子的金屬糊等,且揭示有可於比較低的溫度下進行燒結,但無任何和接合材料中的溶媒與粒子的分離及塗佈穩定性相關的記載,為了實現高的接合強度及塗佈穩定性而有進一步的研究餘地。Furthermore, in recent years, devices including light-emitting elements such as LEDs, semiconductor wafers, and the like have been demanded to increase their output, and there have been cases where higher integration or higher input power has been performed. Therefore, the driving temperature of these devices becomes higher, and the use environment of the bonding material tends to become more severe. Therefore, high bonding strength is required for bonding of light-emitting elements such as LEDs, semiconductor wafers, and the like. In addition, even if it is a bonding material having high bonding strength, if the coating stability is poor, electrical short circuit and contamination of peripheral members may occur. Therefore, a bonding material excellent in coating stability is required. The above-mentioned Patent Documents 1 to 3 disclose metal pastes containing silver nanoparticles, etc., and it is disclosed that sintering can be performed at a relatively low temperature, but there is no separation and coating from the solvent and particles in the bonding material. There is room for further research in the description of cloth stability in order to achieve high bonding strength and coating stability.
本發明是鑑於所述課題而成,其目的在於提供一種於接合用組成物中的溶媒與粒子不分離的情況下塗佈穩定性優異、於比較低的溫度(200℃以下)下燒結、且可獲得高的接合強度的接合用組成物。The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a bonding composition that is excellent in coating stability, sintered at a relatively low temperature (200° C. or lower) without separation of the solvent and particles in the bonding composition, and A bonding composition with high bonding strength can be obtained.
[解決課題之手段] 本發明者等人著眼於為了發揮優異的接合強度而重要的是於接合用組成物的溶媒與粒子不分離的情況下顯示出優異的塗佈穩定性這一情況,發現藉由將被覆金屬粒子的有機物、溶媒的種類及黏度設為特定的範圍,於接合用組成物中的溶媒與金屬粒子不分離的情況下塗佈穩定性優異,進而即便於LED等發光元件、半導體晶片等的接合中使用亦可獲得充分的接合強度,從而完成了本發明。[Means of Solving Problems] The inventors of the present invention paid attention to the fact that, in order to exhibit excellent bonding strength, it is important to exhibit excellent coating stability without separation of the solvent and particles of the bonding composition, and found that by coating metal particles with The organic substance, the type of solvent, and the viscosity are set in a specific range, and the coating stability is excellent when the solvent in the bonding composition does not separate from the metal particles, and it is also used in the bonding of light-emitting elements such as LEDs, semiconductor wafers, etc. The present invention has been completed by obtaining sufficient bonding strength even in use.
即,本發明為一種接合用組成物,其含有:第一金屬粒子,由具有極性基的胺被覆表面且平均粒徑為20 nm~100 nm;第二金屬粒子,平均粒徑為200 nm~500 nm;分散介質;以及高分子分散劑,所述接合用組成物的特徵在於:所述第一金屬粒子與所述第二金屬粒子的重量比率為20:80~80:20,固體成分濃度為90重量%以上,所述分散介質包含二醇,25℃下的黏度為100 mPa・s~300 mPa・s。That is, the present invention is a bonding composition comprising: first metal particles whose surfaces are covered with an amine having a polar group and have an average particle diameter of 20 nm to 100 nm; and second metal particles whose average particle diameter is 200 nm to 100 nm. 500 nm; a dispersion medium; and a polymer dispersant, the bonding composition is characterized in that the weight ratio of the first metal particle to the second metal particle is 20:80 to 80:20, and the solid content concentration 90% by weight or more, the dispersion medium contains diol, and the viscosity at 25°C is 100 mPa・s to 300 mPa・s.
所述第二金屬粒子較佳為表面由具有極性基的胺被覆。The surface of the second metal particle is preferably coated with an amine having a polar group.
所述分散介質較佳為選自由2,4-二乙基-1,5-戊二醇、2-乙基-1,3-己二醇、3-甲基-1,3-丁二醇所組成的群組中的至少一種。The dispersion medium is preferably selected from 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,3-butanediol at least one of the groups.
所述胺較佳為烷氧基胺。The amine is preferably an alkoxyamine.
另外,本發明亦為一種接合用組成物的製備方法,其特徵在於:具有藉由將由具有極性基的胺被覆表面且平均粒徑為20 nm~100 nm的第一金屬粒子、平均粒徑為200 nm~500 nm的第二金屬粒子、分散介質、及高分子分散劑加以混合來製備接合用組成物的步驟,並調配成所述接合用組成物中的固體成分濃度成為90重量%以上,且所述第一金屬粒子與所述第二金屬粒子的重量比率為20:80~80:20,所述分散介質包含二醇,25℃下的黏度被調整為100 mPa・s~300 mPa・s。In addition, the present invention is also a method for producing a composition for bonding, characterized by comprising first metal particles having an average particle diameter of 20 nm to 100 nm by coating the surface with an amine having a polar group and having an average particle diameter of 20 nm to 100 nm. A step of preparing a bonding composition by mixing second metal particles of 200 nm to 500 nm, a dispersion medium, and a polymer dispersant, and preparing the bonding composition so that the solid content concentration in the bonding composition becomes 90% by weight or more, The weight ratio of the first metal particles to the second metal particles is 20:80 to 80:20, the dispersion medium contains diol, and the viscosity at 25°C is adjusted to 100 mPa・s to 300 mPa・ s.
[發明的效果] 根據本發明,可提供一種於接合用組成物中的溶媒與粒子不分離的情況下塗佈穩定性優異、於比較低的溫度(200℃以下)下燒結、且可獲得高的接合強度的接合用組成物及其製備方法。另外,藉由使用此種接合用組成物,可防止接合部的周邊構件的電性短路、污染等,可實現LED等發光元件的長壽命化。[Effect of invention] According to the present invention, it is possible to provide a joint that is excellent in coating stability, sintered at a relatively low temperature (200° C. or lower), and obtains high joint strength without separation of the solvent and particles in the joint composition. Composition and preparation method thereof. In addition, by using such a bonding composition, electrical short-circuiting, contamination, and the like of peripheral members of the bonding portion can be prevented, and the life of light-emitting elements such as LEDs can be extended.
本發明的接合用組成物含有:第一金屬粒子,由具有極性基的胺被覆表面且平均粒徑為20 nm~100 nm;第二金屬粒子,平均粒徑為200 nm~500 nm;分散介質;以及高分子分散劑,所述接合用組成物的特徵在於:所述第一金屬粒子與所述第二金屬粒子的重量比率為20:80~80:20,固體成分濃度為90重量%以上,所述分散介質包含二醇,25℃下的黏度為100 mPa・s~300 mPa・s。The bonding composition of the present invention contains: first metal particles, the surface of which is coated with an amine having a polar group and having an average particle diameter of 20 nm to 100 nm; second metal particles, an average particle diameter of 200 nm to 500 nm; a dispersion medium and a polymer dispersant, wherein the bonding composition is characterized in that the weight ratio of the first metal particle to the second metal particle is 20:80 to 80:20, and the solid content concentration is 90% by weight or more , the dispersion medium contains diol, and the viscosity at 25°C is 100 mPa・s to 300 mPa・s.
所述第一金屬粒子的平均粒徑為20 nm~100 nm。所述接合用組成物於超過200℃的煆燒溫度下亦可使金屬粒子彼此燒結,但藉由將所述第一金屬粒子的平均粒徑設為20 nm~100 nm,而產生熔點下降,即便於比較低的溫度(例如,200℃以下、較佳為150℃左右)下亦可使金屬粒子彼此燒結。另外,可使接合用組成物中的第一金屬粒子的分散性難以產生經時變化。若所述第一金屬粒子的平均粒徑未滿20 nm,則因第一金屬粒子的表面積變大而接合用組成物的黏度變高,處理性降低。另外,於利用有機保護成分被覆第一金屬粒子的表面的情況下,所述有機保護成分量增加,而於煆燒後殘留有機物,燒結體的密度降低,因此接合強度降低。另一方面,若所述第一金屬粒子的平均粒徑超過100 nm,則難以產生熔點下降,於比較低的溫度下金屬粒子彼此難以燒結。所述第一金屬粒子的平均粒徑的較佳的下限為25 nm,較佳的上限為80 nm。The average particle size of the first metal particles is 20 nm to 100 nm. The bonding composition can sinter metal particles with each other at a sintering temperature exceeding 200° C., but by setting the average particle diameter of the first metal particles to be 20 nm to 100 nm, the melting point decreases, Metal particles can be sintered together even at a relatively low temperature (for example, 200° C. or lower, preferably about 150° C.). In addition, the dispersibility of the first metal particles in the bonding composition can be less likely to change with time. When the average particle diameter of the first metal particles is less than 20 nm, the surface area of the first metal particles increases, the viscosity of the bonding composition increases, and the handleability decreases. In addition, when the surface of the first metal particle is coated with an organic protective component, the amount of the organic protective component increases, and the organic matter remains after the calcination, so that the density of the sintered body decreases, and thus the bonding strength decreases. On the other hand, when the average particle diameter of the first metal particles exceeds 100 nm, it is difficult to cause a melting point drop, and it is difficult for the metal particles to sinter each other at a relatively low temperature. The preferred lower limit of the average particle size of the first metal particles is 25 nm, and the preferred upper limit is 80 nm.
本說明書中,所謂「平均粒徑」,為金屬粒子的一次平均粒徑,且是指數量平均粒徑。所述數量平均粒徑例如可對使用掃描式電子顯微鏡(scanning electron microscope,SEM)(例如,日立股份有限公司製造的S-4800型)獲得的圖像使用圖像處理軟體(例如,三谷公司(MITANI CORPORATION),WinROOF)進行算出。另外,金屬粒子的粒徑亦可利用動態光散射法、小角X射線散射法、廣角X射線繞射法進行測定。In this specification, the "average particle size" refers to the primary average particle size of the metal particles, and refers to the number average particle size. The number-average particle size can be obtained, for example, using image processing software (for example, Mitani Corporation ( MITANI CORPORATION), WinROOF) to calculate. In addition, the particle diameter of the metal particles can also be measured by a dynamic light scattering method, a small-angle X-ray scattering method, or a wide-angle X-ray diffraction method.
所述接合用組成物進而含有平均粒徑為200 nm~500 nm的第二金屬粒子。藉由併用平均粒徑為200 nm~500 nm的第二金屬粒子,可提高接合用組成物中的固體成分濃度,可減少第一金屬粒子及第二金屬粒子與分散介質(包含二醇,25℃下的黏度為100 mPa・s~300 mPa・s)的分離。進而,可抑制煆燒時的體積收縮,且難以產生裂紋,從而可獲得密度更高的燒結體。若所述第二金屬粒子的平均粒徑未滿200 nm,則有時無法充分抑制煆燒時的體積收縮。另一方面,若所述第二金屬粒子的平均粒徑超過500 nm,則於利用被接合構件彼此夾持本實施形態的接合用組成物時,有時因粒徑大的金屬粒子而產生間隙,並且接合強度降低。所述第二金屬粒子的平均粒徑的更佳的下限為250 nm,更佳的上限為400 nm。所述第二金屬粒子的平均粒徑可利用與所述第一金屬粒子的平均粒徑相同的方法進行測定。The bonding composition further contains second metal particles having an average particle diameter of 200 nm to 500 nm. By using the second metal particles with an average particle diameter of 200 nm to 500 nm in combination, the solid content concentration in the bonding composition can be increased, and the first metal particles and the second metal particles and the dispersion medium (including diol, 25 The viscosity at ℃ is 100 mPa・s to 300 mPa・s). Furthermore, volume shrinkage during sintering can be suppressed, and cracks are less likely to occur, so that a sintered body having a higher density can be obtained. When the average particle diameter of the second metal particles is less than 200 nm, volume shrinkage during calcination may not be sufficiently suppressed. On the other hand, when the average particle diameter of the second metal particles exceeds 500 nm, gaps may occur due to metal particles having a large particle diameter when the bonding composition of the present embodiment is sandwiched between the members to be joined. , and the bond strength decreases. A more preferable lower limit of the average particle diameter of the second metal particles is 250 nm, and a more preferable upper limit is 400 nm. The average particle diameter of the second metal particles can be measured by the same method as the average particle diameter of the first metal particles.
所述第一金屬粒子的表面由具有極性基的胺被覆。所述胺為與第一金屬粒子的表面的至少一部分鍵結而形成膠體的成分。所述胺無需被覆所述第一金屬粒子的整個表面,只要以可形成膠體的程度被覆第一金屬粒子的表面的至少一部分即可。藉由第一金屬粒子由具有極性基的胺被覆,可提高所述第一金屬粒子的分散穩定性而防止凝聚,若於煆燒時殘存所述胺,則可阻礙金屬粒子彼此的熔接。另外,所述胺於煆燒時蒸發或分解,自第一金屬粒子的表面脫離。The surface of the said 1st metal particle is coat|covered with the amine which has a polar group. The amine is a component that binds to at least a part of the surface of the first metal particle to form a colloid. The amine does not need to coat the entire surface of the first metal particle, but only needs to coat at least a part of the surface of the first metal particle to such an extent that a colloid can be formed. By coating the first metal particles with an amine having a polar group, the dispersion stability of the first metal particles can be improved and aggregation can be prevented, and if the amine remains during calcination, fusion of the metal particles can be inhibited. In addition, the amine evaporates or decomposes during calcination, and is detached from the surface of the first metal particle.
本說明書中,所述極性基為包含電負度大的氧原子或氮原子的原子團,可列舉烷氧基(RO-)、羥基(-OH)、羧基(-COOH)等極性基。於具有極性基的分子間形成氫鍵。因此,若將由具有極性基的胺被覆表面的第一金屬粒子與二醇(分子內具有兩個羥基)加以混合,則於被覆第一金屬粒子的表面的胺中的極性基與二醇之間形成氫鍵,可抑制第一金屬粒子與分散介質的分離。於具有選自由烷氧基、羥基及羧基所組成的群組中的至少一種作為極性基的胺中,源自胺的氮原子的數量較佳為胺以外的官能基的數量以上。另外,所述胺可分別單獨使用,亦可併用兩種以上。In the present specification, the polar group is an atomic group containing a highly electronegative oxygen atom or nitrogen atom, and polar groups such as an alkoxy group (RO-), a hydroxyl group (-OH), and a carboxyl group (-COOH) are exemplified. Forms hydrogen bonds between molecules with polar groups. Therefore, when the first metal particle whose surface is coated with an amine having a polar group and a diol (having two hydroxyl groups in the molecule) are mixed, the polar group and the diol in the amine covering the surface of the first metal particle are mixed. The formation of hydrogen bonds can suppress the separation of the first metal particles and the dispersion medium. In the amine having at least one selected from the group consisting of an alkoxy group, a hydroxyl group, and a carboxyl group as a polar group, the number of nitrogen atoms derived from the amine is preferably more than the number of functional groups other than the amine. In addition, the amines may be used alone or in combination of two or more.
第二金屬粒子的表面的至少一部分由胺等有機保護成分被覆即可,有機保護成分並無特別限定,但較佳為與第一金屬粒子同樣地由具有極性基的胺被覆表面。若第二金屬粒子的表面由具有極性基的胺被覆,則可抑制第二金屬粒子與分散介質的分離。At least a part of the surface of the second metal particle may be coated with an organic protective component such as an amine. The organic protective component is not particularly limited, but the surface is preferably coated with an amine having a polar group as in the case of the first metal particle. When the surface of the second metal particle is coated with an amine having a polar group, separation of the second metal particle and the dispersion medium can be suppressed.
所述具有極性基的胺較佳為包含至少一種的沸點為150℃以下的胺。其原因在於:於接合對象為LED般的發光元件的情況下,要求於比較低的溫度(例如200℃以下)下進行煆燒,但若所述胺的沸點超過150℃,則於比較低的溫度(例如200℃以下)下煆燒接合用組成物時,於燒結體中殘存並未揮發的有機保護成分(具有極性基的胺),產生金屬粒子彼此並未充分燒結的擔憂。亦考慮到所述胺與金屬粒子化學性或物理性鍵結的情況、或變化為陰離子或陽離子的情況,於本實施形態中,所述胺亦可採取源自所述胺的離子、錯合物等狀態。The amine having a polar group preferably contains at least one amine having a boiling point of 150°C or lower. The reason for this is that when the object to be joined is an LED-like light-emitting element, the calcination is required to be performed at a relatively low temperature (for example, 200°C or lower). When the composition for bonding is sintered at a temperature (eg, 200° C. or lower), an organic protective component (amine having a polar group) that does not volatilize remains in the sintered body, and there is a fear that the metal particles are not sufficiently sintered. Considering the case where the amine is chemically or physically bonded to the metal particles, or the case where it is changed to an anion or a cation, in this embodiment, the amine can also take an ion derived from the amine, a complex state of things.
所述沸點為150℃以下的具有極性基的胺可為直鏈狀亦可為分支鏈狀,另外,亦可具有側鏈。作為具體例,較佳為烷氧基胺,其中更佳為3-甲氧基丙基胺及/或3-乙氧基丙基胺。The amine having a polar group having a boiling point of 150° C. or lower may be linear or branched, and may have a side chain. As a specific example, an alkoxyamine is preferable, and among them, 3-methoxypropylamine and/or 3-ethoxypropylamine are more preferable.
再者,第二金屬粒子的表面亦可由與被覆所述第一金屬粒子的表面的具有極性基的胺相同的有機保護成分被覆。被覆所述第二金屬粒子的表面的有機保護成分可與被覆所述第一金屬粒子的表面的具有極性基的胺相同,亦可不同。In addition, the surface of the second metal particle may be coated with the same organic protective component as the amine having a polar group that coats the surface of the first metal particle. The organic protective component covering the surface of the second metal particle may be the same as or different from the amine having a polar group covering the surface of the first metal particle.
於第二金屬粒子的表面由與被覆第一金屬粒子的表面的所述具有極性基的胺不同的胺被覆的情況下,關於被覆第二金屬粒子的表面的胺,根據與所述相同的理由,亦較佳為包含至少一種的沸點為150℃以下的胺。另外,關於被覆第二金屬粒子的胺,可為直鏈狀亦可為分支狀,亦可具有側鏈。When the surface of the second metal particle is coated with an amine different from the amine having a polar group that coats the surface of the first metal particle, the amine that coats the surface of the second metal particle is for the same reason as described above. , it is also preferable to contain at least one amine whose boiling point is 150°C or lower. Moreover, the amine which coats a 2nd metal particle may be linear or branched, and may have a side chain.
接合用組成物中的胺的含量較佳為0.1重量%~15重量%。再者,接合用組成物中的胺的含量是指被覆第一金屬粒子的表面的具有極性基的胺的量與被覆第二金屬粒子的表面的胺的量的合計值。若接合用組成物中的有機保護成分的含量為0.1重量%以上,則存在所獲得的接合用組成物的導電性變良好的傾向,若為15重量%以下,則存在接合用組成物的分散穩定性良好的傾向。所述有機保護成分的含量的更佳的下限為0.2重量%,更佳的上限為5重量%,進而佳的下限為0.3重量%,進而佳的上限為4重量%。所述有機保護成分的含量可利用熱重分析進行測定。The content of the amine in the bonding composition is preferably 0.1% by weight to 15% by weight. In addition, the content of the amine in the composition for bonding refers to the total value of the amount of the amine having a polar group covering the surface of the first metal particle and the amount of the amine covering the surface of the second metal particle. When the content of the organic protective component in the bonding composition is 0.1 wt % or more, the conductivity of the obtained bonding composition tends to be good, and when it is 15 wt % or less, the bonding composition is dispersed Tendency to be good in stability. A more preferable lower limit of the content of the organic protective component is 0.2 wt %, a more preferable upper limit is 5 wt %, a further preferable lower limit is 0.3 wt %, and a further preferable upper limit is 4 wt %. The content of the organic protective component can be determined by thermogravimetric analysis.
所述第一金屬粒子及所述第二金屬粒子並無特別限定,例如可列舉:金、銀、銅、鎳、鉍、錫及鉑族元素(釕、銠、鈀、鋨、銥及鉑)中的至少一種。作為所述金屬,較佳為選自由金、銀、銅、鎳、鉍、錫或鉑族元素所組成的群組中的至少一種金屬的粒子,進而較佳為銅或離子化傾向比銅小的(更惰性的)金屬、即金、鉑、銀及銅中的至少一種。該些金屬可單獨使用,亦可併用兩種以上來使用,作為併用的方法,有使用包含多種金屬的合金粒子的情況、或使用具有核-殼結構或多層結構的金屬粒子的情況。The first metal particle and the second metal particle are not particularly limited, and examples thereof include gold, silver, copper, nickel, bismuth, tin, and platinum group elements (ruthenium, rhodium, palladium, osmium, iridium, and platinum) at least one of them. The metal is preferably a particle of at least one metal selected from the group consisting of gold, silver, copper, nickel, bismuth, tin or platinum group elements, and more preferably copper or has a smaller ionization tendency than copper (more inert) metals, namely at least one of gold, platinum, silver and copper. These metals may be used alone or in combination of two or more. As a method of combined use, alloy particles containing a plurality of metals are used, or metal particles having a core-shell structure or a multilayer structure are used.
於使用銀微粒子作為所述第一金屬粒子及所述第二金屬粒子的情況下,使用本實施形態的接合用組成物形成的燒結體(燒結層)的導電率良好。藉由在銀微粒子中併用包含其他金屬的粒子,可難以引起遷移。作為所述「其他金屬」,較佳為所述離子化傾向比氫更惰性的金屬、即金、銅、鉑、鈀。When silver fine particles are used as the first metal particles and the second metal particles, the electrical conductivity of the sintered body (sintered layer) formed using the bonding composition of the present embodiment is good. It becomes difficult to cause migration by using the particle|grains containing other metal together with silver microparticles|fine-particles. The "other metal" is preferably a metal whose ionization tendency is more inert than hydrogen, that is, gold, copper, platinum, and palladium.
所述第二金屬粒子可使用種類與所述第一金屬粒子中例示的金屬粒子相同的金屬粒子。構成所述第二金屬粒子的金屬可與所述第一金屬粒子相同,亦可不同。As the second metal particles, the same kind of metal particles as the metal particles exemplified in the first metal particles can be used. The metal constituting the second metal particle may be the same as or different from the first metal particle.
所述第一金屬粒子與所述第二金屬粒子的重量比率為20:80~80:20。藉此,可實現低溫燒結性並且可進一步提高接合強度。若所述第一金屬粒子的重量相對於所述第二金屬粒子80重量份而未滿20重量份,則接合用組成物中的平均粒徑為20 nm~100 nm的第一金屬粒子的比例變低,有時於比較低的溫度下金屬粒子彼此難以燒結。另一方面,若所述第一金屬粒子的重量相對於所述第二金屬粒子20重量份而超過80重量份,則煆燒時的體積收縮變大,燒結體中容易產生裂紋,因此存在接合強度降低的傾向。所述第一金屬粒子與所述第二金屬粒子的更佳的重量比率為30:70~60:40。若所述第二金屬粒子的重量較所述第一金屬粒子的重量而言變多,則接合用組成物的流動性降低且處理性降低,另一方面,存在重量減少率降低的傾向,因此所述第一金屬粒子與所述第二金屬粒子的重量比率可考慮到處理性與重量減少率的平衡來決定。The weight ratio of the first metal particles to the second metal particles is 20:80˜80:20. Thereby, low-temperature sinterability can be achieved, and bonding strength can be further improved. If the weight of the first metal particles is less than 20 parts by weight relative to 80 parts by weight of the second metal particles, the ratio of the first metal particles having an average particle diameter of 20 nm to 100 nm in the bonding composition If it becomes lower, it may be difficult for metal particles to sinter each other at a relatively low temperature. On the other hand, if the weight of the first metal particles exceeds 80 parts by weight with respect to 20 parts by weight of the second metal particles, the volume shrinkage during sintering becomes large, and cracks tend to occur in the sintered body, resulting in bonding. Tendency to decrease in strength. A more preferable weight ratio of the first metal particles to the second metal particles is 30:70 to 60:40. When the weight of the second metal particles is larger than the weight of the first metal particles, the fluidity of the bonding composition is lowered and the handleability is lowered. On the other hand, the weight reduction rate tends to be lowered. The weight ratio of the first metal particle to the second metal particle may be determined in consideration of the balance between the handleability and the weight reduction rate.
所述接合用組成物的固體成分濃度為90重量%以上。若固體成分濃度未滿90重量%,則接合用組成物中的金屬粒子的含量變少,因此燒結體的密度變低,產生無法獲得充分的接合強度的可能性。The solid content concentration of the bonding composition is 90% by weight or more. If the solid content concentration is less than 90% by weight, the content of the metal particles in the bonding composition decreases, so the density of the sintered body decreases, and there is a possibility that sufficient bonding strength cannot be obtained.
接合用組成物含有分散介質,所述分散介質包含二醇,25℃下的黏度為100 mPa・s~300 mPa・s。藉由含有此種特定的分散介質,可防止所述接合用組成物中的分散介質與金屬粒子的分離,提高所述接合用組成物的塗佈穩定性。分散介質中的沈降的金屬粒子的沈降速度依據斯托克斯(Stokes)定律,因此藉由將分散介質於25℃下的黏度設為100 mPa・s以上,可較佳地防止金屬粒子的沈降。另外,藉由將分散介質於25℃下的黏度設為300 mPa・s以下,可確保接合用組成物的處理性。The bonding composition contains a dispersion medium containing diol and has a viscosity of 100 mPa・s to 300 mPa・s at 25°C. By containing such a specific dispersion medium, separation of the dispersion medium and the metal particles in the bonding composition can be prevented, and the coating stability of the bonding composition can be improved. The sedimentation velocity of the settled metal particles in the dispersion medium is based on Stokes' law. Therefore, by setting the viscosity of the dispersion medium at 25°C to 100 mPa・s or more, the sedimentation of the metal particles can be better prevented. . In addition, by setting the viscosity of the dispersion medium at 25°C to 300 mPa·s or less, the handleability of the bonding composition can be ensured.
所述分散介質相對於接合用組成物整體的濃度為1.0重量%以上且8.5重量%以下。若所述分散介質的濃度未滿1.0重量%,則接合用組成物的剪切黏度過高而處理性差,難以塗敷於被接合構件。另一方面,若所述分散介質的濃度超過8.5重量%,則接合用組成物中的流體密度上升,金屬粒子的沈降速度上升,因此無法有效果地防止接合用組成物中的分散介質與金屬粒子的分離,產生塗佈穩定性變低的可能性。另外,接合用組成物中的金屬粒子的含量變少,因此燒結體的密度變低,產生無法獲得充分的接合強度的可能性。The concentration of the dispersion medium with respect to the entire bonding composition is 1.0% by weight or more and 8.5% by weight or less. If the concentration of the dispersion medium is less than 1.0% by weight, the shear viscosity of the composition for joining is too high, and the handleability is poor, making it difficult to apply the composition to the member to be joined. On the other hand, when the concentration of the dispersion medium exceeds 8.5 wt %, the fluid density in the bonding composition increases and the sedimentation velocity of the metal particles increases, so that the dispersion medium and the metal in the bonding composition cannot be effectively prevented from Separation of particles may lead to lower coating stability. In addition, since the content of the metal particles in the bonding composition decreases, the density of the sintered body decreases, and there is a possibility that sufficient bonding strength cannot be obtained.
所述分散介質於25℃下的黏度為100 mPa・s~300 mPa・s即可,可使用各種二醇。具體而言,所述分散介質較佳為包含選自由2,4-二乙基-1,5-戊二醇、2-乙基-1,3-己二醇、3-甲基-1,3-丁二醇所組成的群組中的至少一種。再者,本說明書中25℃下的黏度為藉由利用振動式黏度計測定25℃的分散介質而獲得的值。作為振動式黏度計,例如可使用賽科尼可(Sekonic)(股)製造的VM-10A等,測定只要使液體(分散介質)浸漬於振子中進行即可。The viscosity of the dispersion medium at 25°C may be 100 mPa・s to 300 mPa・s, and various diols can be used. Specifically, the dispersion medium preferably contains a substance selected from the group consisting of 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1, At least one of the group consisting of 3-butanediol. In addition, the viscosity at 25 degreeC in this specification is the value obtained by measuring the dispersion medium at 25 degreeC with a vibration viscometer. As the vibrating viscometer, for example, VM-10A manufactured by Sekonic Co., Ltd. can be used, and the measurement may be performed by immersing a liquid (dispersion medium) in a vibrator.
相對於接合用組成物整體的二醇的濃度較佳為2重量%以上且8重量%以下。於接合用組成物中包含兩種以上的二醇的情況下,所述二醇的濃度為根據所有二醇的含量導出的值。其原因在於:藉由相對於接合用組成物整體的二醇的濃度處於所述特定的範圍,可有效果地防止金屬粒子與溶媒的分離,提高接合用組成物的塗佈穩定性。The concentration of the diol with respect to the entire bonding composition is preferably 2% by weight or more and 8% by weight or less. When two or more kinds of diols are contained in the bonding composition, the concentration of the diols is a value derived from the content of all the diols. The reason for this is that when the concentration of the diol with respect to the entire bonding composition is within the above-described specific range, separation of the metal particles and the solvent can be effectively prevented, and the coating stability of the bonding composition can be improved.
所述分散介質以25℃下的黏度成為100 mPa・s~300 mPa・s的方式,除包含二醇以外,亦可包含異十三烷醇、及2,2,4-三甲基戊烷-1,3-二醇單異丁酸酯(別名:醇酯-12(texanol))等化合物。所述分散介質較佳為包含二醇與異十三烷醇及/或2,2,4-三甲基戊烷-1,3-二醇單異丁酸酯(別名:醇酯-12)。另外,所述分散介質較佳為調配有二醇與異十三烷醇及/或2,2,4-三甲基戊烷-1,3-二醇單異丁酸酯(別名:醇酯-12)而成者,25℃下的黏度被調整為100 mPa・s~300 mPa・s。The dispersion medium may contain, in addition to diol, isotridecanol and 2,2,4-trimethylpentane so that the viscosity at 25°C becomes 100 mPa・s to 300 mPa・s -1,3-Diol monoisobutyrate (alias: alcohol ester-12 (texanol)) and other compounds. The dispersion medium preferably contains diol and isotridecanol and/or 2,2,4-trimethylpentane-1,3-diol monoisobutyrate (alias: alcohol ester-12) . In addition, the dispersion medium is preferably prepared with diol, isotridecanol and/or 2,2,4-trimethylpentane-1,3-diol monoisobutyrate (alias: alcohol ester) -12), the viscosity at 25°C is adjusted to 100 mPa・s to 300 mPa・s.
本實施形態的接合用組成物進而含有高分子分散劑。藉此,可提高金屬粒子的分散性。另外,藉由使高分子分散劑吸附於第一金屬粒子及/或第二金屬粒子的粒子表面,可均勻地混合金屬粒子與分散介質,進而可防止金屬粒子與分散介質(包含二醇,25℃下的黏度為100 mPa・s~300 mPa・s)的分離。The bonding composition of the present embodiment further contains a polymer dispersant. Thereby, the dispersibility of metal particles can be improved. In addition, by adsorbing the polymer dispersant on the particle surfaces of the first metal particles and/or the second metal particles, the metal particles and the dispersion medium can be uniformly mixed, and the metal particles and the dispersion medium (including glycol, 25 The viscosity at ℃ is 100 mPa・s to 300 mPa・s).
作為所述高分子分散劑,亦可使用市售者。作為所述市售品,例如可列舉:索努帕斯(SOLSPERSE)11200、索努帕斯13940、索努帕斯16000、索努帕斯17000、索努帕斯18000、索努帕斯20000、索努帕斯21000、索努帕斯24000、索努帕斯26000、索努帕斯27000、索努帕斯28000(日本路博潤(Lubrizol)(股)製造);迪斯帕畢克(DISPERBYK)118、迪斯帕畢克142、迪斯帕畢克160、迪斯帕畢克161、迪斯帕畢克162、迪斯帕畢克163、迪斯帕畢克166、迪斯帕畢克170、迪斯帕畢克180、迪斯帕畢克182、迪斯帕畢克184、迪斯帕畢克190、迪斯帕畢克2155(日本畢克化學(BYK-Chemie Japan)(股)製造);埃夫卡(EFKA)-46、EFKA-47、EFKA-48、EFKA-49(埃夫卡(EFKA)化學公司製造);聚合物(polymer)100、聚合物120、聚合物150、聚合物400、聚合物401、聚合物402、聚合物403、聚合物450、聚合物451、聚合物452、聚合物453(埃夫卡(EFKA)化學公司製造);阿吉斯帕(Ajisper)PB711、阿吉斯帕PA111、阿吉斯帕PB811、阿吉斯帕PW911(味之素公司製造);弗洛倫(Flowlen)DOPA-15B、弗洛倫DOPA-22、弗洛倫DOPA-17、弗洛倫TG-730W、弗洛倫G-700、弗洛倫TG-720W(共榮社化學工業(股)製造)等。As the polymer dispersant, a commercially available one can also be used. As said commercial item, Sonopas (SOLSPERSE) 11200, Sonopas 13940, Sonopas 16000, Sonopas 17000, Sonopas 18000, Sonopas 20000, Sonupas 21000, Sonupas 24000, Sonupas 26000, Sonupas 27000, Sonupas 28000 (manufactured by Lubrizol, Japan); DISPERBYK ) 118, Dispaic 142, Dispaic 160, Dispaic 161, Dispaic 162, Dispaic 163, Dispaic 166, Dispaic 170, DISPARPIC 180, DISPARPIC 182, DISPARPIC 184, DISPARPIC 190, DISPARPIC 2155 (BYK-Chemie Japan) (stock) manufacture); EFKA-46, EFKA-47, EFKA-48, EFKA-49 (manufactured by EFKA Chemicals); polymer 100, polymer 120, polymer 150, Polymer 400, Polymer 401, Polymer 402, Polymer 403, Polymer 450, Polymer 451, Polymer 452, Polymer 453 (manufactured by EFKA Chemicals); Ajisper PB711, Ajispa PA111, Ajispa PB811, Ajispa PW911 (manufactured by Ajinomoto Co.); Floren DOPA-15B, Floren DOPA-22, Floren DOPA-17 , Floren TG-730W, Floren G-700, Floren TG-720W (manufactured by Gongrongshe Chemical Industry (stock)) and so on.
就低溫燒結性的觀點而言,所述高分子分散劑較佳為索努帕斯11200、索努帕斯13940、索努帕斯16000、索努帕斯17000、索努帕斯18000、索努帕斯21000、索努帕斯28000、迪斯帕畢克118或迪斯帕畢克190。From the viewpoint of low-temperature sinterability, the polymer dispersant is preferably Sonopas 11200, Sonopas 13940, Sonopas 16000, Sonopas 17000, Sonopas 18000, Sonopas Paz 21000, Sonopas 28000, Dispapic 118 or Dispapic 190.
接合用組成物中的所述高分子分散劑的含量較佳為0.01重量%~15重量%。若所述高分子分散劑的含量為0.01重量%以上,則存在所獲得的接合用組成物的分散穩定性變良好的傾向,若為15重量%以下,則存在接合用組成物的導電性變良好的傾向。所述高分子分散劑的更佳的下限為0.1重量%,更佳的上限為5重量%,進而佳的下限為0.2重量%,進而佳的上限為4重量%。The content of the polymer dispersant in the bonding composition is preferably 0.01% by weight to 15% by weight. When the content of the polymer dispersing agent is 0.01 wt % or more, the dispersion stability of the obtained joining composition tends to become favorable, and when it is 15 wt % or less, the electrical conductivity of the joining composition tends to deteriorate. good inclination. A more preferable lower limit of the polymer dispersant is 0.1 wt %, a more preferable upper limit is 5 wt %, a further preferable lower limit is 0.2 wt %, and a further preferable upper limit is 4 wt %.
本實施形態的接合用組成物除添加所述成分以外,亦可於無損本發明的效果的範圍內添加例如發揮作為黏合劑的作用的寡聚物成分、樹脂成分、有機溶劑(可使固體成分的一部分溶解或分散)、界面活性劑、增稠劑或表面張力調整劑等任意成分以賦予與使用目的相應的適度的黏性、密接性、乾燥性或印刷性等功能。作為所述任意成分,並無特別限定。In addition to the above-mentioned components, the bonding composition of the present embodiment may contain, for example, an oligomer component, a resin component, and an organic solvent (which may be a solid component) that function as a binder within a range that does not impair the effects of the present invention. (part of the dissolved or dispersed), surfactants, thickeners, surface tension adjusters and other optional components to impart functions such as appropriate viscosity, adhesion, drying, or printability according to the purpose of use. It does not specifically limit as said arbitrary component.
作為所述樹脂成分,例如可列舉:聚酯系樹脂、嵌段異氰酸酯等聚胺基甲酸酯系樹脂、聚丙烯酸酯系樹脂、聚丙烯醯胺系樹脂、聚醚系樹脂、三聚氰胺系樹脂、萜烯系樹脂等,該些可分別單獨使用,亦可併用兩種以上。Examples of the resin component include polyester-based resins, polyurethane-based resins such as blocked isocyanates, polyacrylate-based resins, polyacrylamide-based resins, polyether-based resins, melamine-based resins, Terpene-based resins and the like may be used alone or in combination of two or more.
作為所述有機溶劑,將作為所述分散介質而列舉者除外,例如可列舉:甲基醇、乙基醇、正丙基醇、2-丙基醇、1,2,6-己烷三醇、1-乙氧基-2-丙醇、2-丁氧基乙醇、乙二醇、二乙二醇、三乙二醇、重量平均分子量為200以上且1,000以下的範圍內的聚乙二醇、丙二醇、二丙二醇、三丙二醇、重量平均分子量為300以上且1,000以下的範圍內的聚丙二醇、N,N-二甲基甲醯胺、二甲基亞碸、N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、甘油、丙酮等,該些可分別單獨使用,亦可併用兩種以上。As the organic solvent, excluding those listed as the dispersion medium, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, 2-propyl alcohol, and 1,2,6-hexanetriol are exemplified. , 1-ethoxy-2-propanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol with a weight average molecular weight of 200 or more and 1,000 or less , propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol with a weight average molecular weight of 300 or more and 1,000 or less, N,N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrole Peridone, N,N-dimethylacetamide, glycerol, acetone, etc. may be used alone or in combination of two or more.
作為所述增稠劑,例如可列舉:黏土、膨潤土(bentonite)或鋰膨潤石(hectorite)等黏土礦物、例如聚酯系乳液樹脂、丙烯酸系乳液樹脂、聚胺基甲酸酯系乳液樹脂或嵌段異氰酸酯等乳液、甲基纖維素、羧基甲基纖維素、羥基乙基纖維素、羥基丙基纖維素、羥基丙基甲基纖維素等纖維素衍生物、三仙膠(xanthan gum)或瓜爾膠(guar gum)等多糖類等,該些可分別單獨使用,亦可併用兩種以上。Examples of the thickener include clay minerals such as clay, bentonite, and hectorite, polyester-based emulsion resins, acrylic-based emulsion resins, polyurethane-based emulsion resins, or Blocked isocyanate and other emulsions, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and other cellulose derivatives, xanthan gum or Polysaccharides such as guar gum and the like may be used alone or in combination of two or more.
所述界面活性劑並無特別限定,可使用陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑的任一種,例如可列舉烷基苯磺酸鹽、四級銨鹽等。因以少量的添加量便獲得效果,因此較佳為氟系界面活性劑。The surfactant is not particularly limited, and any of anionic surfactants, cationic surfactants, and nonionic surfactants can be used, and examples thereof include alkylbenzenesulfonates, quaternary ammonium salts, and the like. Since the effect is obtained with a small amount of addition, a fluorine-based surfactant is preferred.
於本實施形態的接合用組成物中,所述第一金屬粒子較佳為作為金屬膠體粒子而存在。關於所述金屬膠體粒子的形態,例如可列舉胺附著於第一金屬粒子的表面的一部分而構成的金屬膠體粒子、將所述第一金屬粒子作為核且其表面由具有極性基的胺被覆而構成的金屬膠體粒子、該些混合存在而構成的金屬膠體粒子等,並無特別限定。其中,較佳為將第一金屬粒子作為核且其表面由具有極性基的胺被覆而構成的金屬膠體粒子。所述第二金屬粒子亦較佳為作為將第二金屬粒子作為核且其表面由具有極性基的胺被覆的金屬膠體粒子而存在。In the bonding composition of the present embodiment, the first metal particles are preferably present as metal colloid particles. The form of the metal colloid particle includes, for example, a metal colloid particle in which an amine adheres to a part of the surface of the first metal particle, a metal colloid particle in which the first metal particle is used as a core and whose surface is coated with an amine having a polar group. The constituted metal colloid particles, the metal colloid particles constituted by mixing these, and the like are not particularly limited. Among them, metal colloid particles in which the first metal particle is used as a core and the surface thereof is covered with an amine having a polar group are preferred. The second metal particle is also preferably present as a metal colloid particle having the second metal particle as a core and whose surface is coated with an amine having a polar group.
接合用組成物的剪切黏度只要於無損本發明的效果的範圍內適宜調整即可,25℃下的剪切黏度較佳為於剪切速度10 s-1 下為15 Pa·S~120 Pa·S。藉由設為所述範圍,例如可於將LED等發光元件、半導體晶片等接合於基板的用途、將該些基板進而接合於放熱構件的用途中較佳地使用。所述剪切黏度的更佳的下限為25 Pa·S,更佳的上限為100 Pa·S。 所述剪切黏度的調整可藉由金屬粒子的粒徑的調整、有機物的含量的調整、分散介質以及其他成分的添加量的調整、各成分的調配比的調整、增稠劑的添加等來進行。所述剪切黏度可利用錐板(cone plate)型黏度計(例如,安東帕(Anton Paar)公司製造的流變儀(Rheometer)MCR301)進行測定。The shear viscosity of the bonding composition may be appropriately adjusted within a range that does not impair the effects of the present invention, and the shear viscosity at 25°C is preferably 15 Pa·S to 120 Pa at a shear rate of 10 s -1 ·S. By setting it as the said range, for example, it can be used suitably for the use which joins light emitting elements, such as LED, a semiconductor wafer, etc. to a board|substrate, and these board|substrates are further bonded to a heat radiating member. A more preferable lower limit of the shear viscosity is 25 Pa·S, and a more preferable upper limit is 100 Pa·S. The shear viscosity can be adjusted by adjusting the particle size of the metal particles, adjusting the content of organic matter, adjusting the addition amount of the dispersion medium and other components, adjusting the mixing ratio of each component, adding a thickener, etc. conduct. The shear viscosity can be measured using a cone plate viscometer (eg, Rheometer MCR301 manufactured by Anton Paar).
利用接合用組成物接合被接合構件彼此時的接合強度較佳為20 MPa~150 MPa。若接合強度為20 MPa~150 MPa,則可於LED等發光元件、半導體晶片等與基板的接合、所述基板與放熱構件的接合中較佳地使用。所述接合強度的更佳的下限為30 MPa,進而佳的下限為50 MPa。所述接合強度可藉由如下方式評價:將接合用組成物塗敷於其中一被接合構件上,貼附另一被接合構件後進行煆燒,對所獲得的積層體使用例如接合試驗機(bond tester)(力世科(rhesca)公司製造)進行接合強度試驗。The bonding strength when the members to be bonded are bonded by the bonding composition is preferably 20 MPa to 150 MPa. When the bonding strength is 20 MPa to 150 MPa, it can be preferably used for bonding of light-emitting elements such as LEDs, semiconductor wafers, and the like to a substrate, and bonding of the substrate and a heat radiating member. A more preferable lower limit of the bonding strength is 30 MPa, and a further preferable lower limit is 50 MPa. The bonding strength can be evaluated by applying the bonding composition to one of the members to be bonded, attaching the other member to be bonded, and then sintering, and using, for example, a bonding tester ( A bond tester (manufactured by Rhesca) was used to conduct a bond strength test.
本實施形態的接合用組成物具有優異的熱循環可靠性。藉由所述熱循環可靠性良好,亦可於驅動溫度高的器件的製造中的、LED等發光元件、半導體晶片等的接合中較佳地使用。所述熱循環可靠性例如可藉由如下方式評價:將燒結接合用組成物與被接合構件而成的積層體於大氣環境下、-40℃及150℃下各保持10分鐘,將該操作設為一個循環,並進行500個循環的熱循環試驗。所述熱循環試驗例如可使用冷熱衝擊試驗機(優泰克(Futec)公司製造)進行。相對於積層體的初期強度的、熱循環試驗後的積層體的接合強度的降低率較佳為未滿20%,更佳為未滿5%。The bonding composition of the present embodiment has excellent thermal cycle reliability. Since the thermal cycle reliability is good, it can also be suitably used in the manufacture of devices with high drive temperatures, in the bonding of light-emitting elements such as LEDs, and semiconductor wafers. The thermal cycle reliability can be evaluated, for example, by holding the laminated body of the sintered bonding composition and the member to be bonded in an atmospheric environment at -40° C. and 150° C. for 10 minutes each, and setting the operation. For one cycle, a thermal cycle test of 500 cycles was performed. The thermal cycle test can be performed using, for example, a thermal shock tester (manufactured by Futec). The reduction rate of the bonding strength of the laminate after the thermal cycle test with respect to the initial strength of the laminate is preferably less than 20%, more preferably less than 5%.
另外,本發明的實施形態之一的接合用組成物的製備方法的特徵在於:具有藉由將由具有極性基的胺被覆表面且平均粒徑為20 nm~100 nm的第一金屬粒子、由具有極性基的胺被覆且平均粒徑為200 nm~500 nm的第二金屬粒子、分散介質、及高分子分散劑加以混合來製備接合用組成物的步驟,並調配成所述接合用組成物中的固體成分濃度成為90重量%以上,且所述第一金屬粒子與所述第二金屬粒子的重量比率為20:80~80:20,所述分散介質包含二醇,25℃下的黏度被調整為100 mPa・s~300 mPa・s。In addition, a method for producing a composition for bonding according to one embodiment of the present invention is characterized by comprising the first metal particles having an average particle diameter of 20 nm to 100 nm by coating the surface with an amine having a polar group, and having a A step of preparing a composition for bonding by mixing second metal particles with an amine-coated polar group and an average particle diameter of 200 nm to 500 nm, a dispersion medium, and a polymer dispersant to prepare a composition for bonding, and preparing the composition for bonding The solid content concentration is 90% by weight or more, the weight ratio of the first metal particles to the second metal particles is 20:80 to 80:20, the dispersion medium contains diol, and the viscosity at 25°C is Adjust to 100 mPa・s to 300 mPa・s.
(接合用組成物的製備) 為了製造本實施形態的接合用組成物,製備作為主要成分的由「具有極性基的胺」被覆的金屬粒子(金屬膠體粒子)。(Preparation of composition for bonding) In order to manufacture the composition for bonding of the present embodiment, metal particles (metal colloid particles) coated with "amine having a polar group" as a main component are prepared.
再者,「具有極性基的胺」量及重量減少率的調整並無特別限定,但簡便的是進行加熱來調整。亦可藉由調整製作金屬粒子時添加的「具有極性基的胺」的量來進行。亦可改變金屬粒子調整後的清洗條件或次數。另外,加熱可利用烘箱或蒸發器等進行。加熱溫度只要為50℃~300℃左右的範圍即可,加熱時間只要為幾分鐘~幾小時即可。加熱亦可於減壓下進行。藉由在減壓下加熱,可於更低的溫度下進行有機物量的調整。於在常壓下進行的情況下,可於大氣中亦可於惰性環境中進行。進而,為了對有機成分量進行微調,亦可之後加入胺。In addition, although the adjustment of the amount of "amine which has a polar group" and the weight reduction rate is not specifically limited, It is easy to adjust by heating. It can also be performed by adjusting the amount of the "amine having a polar group" added when producing metal particles. It is also possible to change the cleaning conditions or times after the adjustment of the metal particles. In addition, heating can be performed using an oven, an evaporator, or the like. The heating temperature may be in the range of about 50° C. to 300° C., and the heating time may be in the range of several minutes to several hours. Heating can also be performed under reduced pressure. The amount of organic matter can be adjusted at a lower temperature by heating under reduced pressure. In the case of carrying out under normal pressure, it can be carried out in the atmosphere or in an inert environment. Furthermore, in order to finely adjust the amount of organic components, an amine may be added later.
作為製備本實施形態的由「具有極性基的胺」被覆的金屬粒子的方法,並無特別限定,例如可列舉製備包含金屬粒子的分散液,之後進行該分散液的清洗的方法等。作為製備包含金屬粒子的分散液的步驟,例如如下述般將溶解於溶媒中的金屬鹽(或金屬離子)還原即可,作為還原程序,只要採用基於化學還原法的程序即可。另外,亦可使用金屬胺錯合物法(詳情後述)。The method of preparing the metal particles coated with the "amine having a polar group" according to the present embodiment is not particularly limited, and examples thereof include a method of preparing a dispersion liquid containing metal particles and then washing the dispersion liquid. As a step of preparing a dispersion liquid containing metal particles, for example, a metal salt (or metal ion) dissolved in a solvent may be reduced as described below, and as a reduction procedure, a procedure based on a chemical reduction method may be employed. In addition, a metal amine complex method (details will be described later) can also be used.
即,所述般的由「具有極性基的胺」被覆的金屬粒子可藉由將包含構成金屬粒子的金屬的金屬鹽、「具有極性基的胺」、所述高分子分散劑、及所述分散介質的原料液還原來製備。再者,原料液的成分的一部分可不溶解而分散,另外亦可包含水。That is, the metal particles coated with the above-mentioned "amine having a polar group" can be prepared by combining the metal salt of the metal constituting the metal particle, the "amine having a polar group", the polymer dispersant, and the It is prepared by reducing the stock solution of the dispersion medium. Furthermore, a part of the components of the raw material liquid may be dispersed without dissolving, and may also contain water.
藉由該還原,可獲得「具有極性基的胺」附著於金屬粒子的表面的至少一部分上的金屬膠體粒子。藉由該金屬膠體粒子於後述的步驟中添加至分散介質中,亦可獲得包含金屬膠體分散液的接合用組成物。By this reduction, a metal colloid particle in which the "amine having a polar group" adheres to at least a part of the surface of the metal particle can be obtained. By adding this metal colloid particle to a dispersion medium in the process mentioned later, the composition for joining containing a metal colloid dispersion liquid can also be obtained.
作為用於獲得由「具有極性基的胺」被覆的金屬粒子的起始材料,可使用各種公知的金屬鹽或其水合物,可列舉:例如硝酸銀、硫酸銀、氯化銀、氧化銀、乙酸銀、草酸銀、甲酸銀、亞硝酸銀、氯酸銀、硫化銀等銀鹽;例如氯金酸、氯化金鉀、氯化金鈉等金鹽;例如氯鉑酸、氯化鉑、氧化鉑、氯鉑酸鉀等鉑鹽;例如硝酸鈀、乙酸鈀、氯化鈀、氧化鈀、硫酸鈀等鈀鹽等,但只要可溶解於適當的分散介質中且能夠還原,則並無特別限定。另外,該些可單獨使用亦可併用多種。As a starting material for obtaining metal particles coated with "amine having a polar group", various known metal salts or hydrates thereof can be used, and examples thereof include silver nitrate, silver sulfate, silver chloride, silver oxide, and acetic acid. Silver, silver oxalate, silver formate, silver nitrite, silver chlorate, silver sulfide and other silver salts; such as chloroauric acid, gold potassium chloride, gold sodium chloride and other gold salts; such as chloroplatinic acid, platinum chloride, oxide Platinum salts such as platinum and potassium chloroplatinate; for example, palladium salts such as palladium nitrate, palladium acetate, palladium chloride, palladium oxide, palladium sulfate, etc., but are not particularly limited as long as they can be dissolved in a suitable dispersion medium and can be reduced . In addition, these may be used alone or in combination.
另外,於所述原料液中還原該些金屬鹽的方法並無特別限定,例如可列舉使用還原劑的方法、照射紫外線等光、電子射束、超音波或熱能的方法等。其中,就操作容易的觀點而言,較佳為使用還原劑的方法。The method of reducing these metal salts in the raw material liquid is not particularly limited, and examples thereof include a method of using a reducing agent, a method of irradiating light such as ultraviolet rays, electron beams, ultrasonic waves, or thermal energy. Among them, a method using a reducing agent is preferred from the viewpoint of easy handling.
作為所述還原劑,可列舉:例如二甲基胺基乙醇、甲基二乙醇胺、三乙醇胺、菲尼酮(phenidone)、肼等胺化合物;例如硼氫化鈉、碘化氫、氫氣等氫化合物;例如一氧化碳、亞硫酸等氧化物;例如硫酸亞鐵、氧化鐵、富馬酸鐵、乳酸鐵、草酸鐵、硫化鐵、乙酸錫、氯化錫、二磷酸錫、草酸錫、氧化錫、硫酸錫等低原子價金屬鹽;例如乙二醇、甘油、甲醛、對苯二酚、五倍子酚、單寧、單寧酸、水楊酸、D-葡萄糖等糖等,只要可溶解於分散介質中並將所述金屬鹽還原,則並無特別限定。於使用所述還原劑的情況下,可施加光及/或熱來促進還原反應。Examples of the reducing agent include amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone, and hydrazine; and hydrogen compounds such as sodium borohydride, hydrogen iodide, and hydrogen gas. ; Oxides such as carbon monoxide, sulfurous acid, etc.; such as ferrous sulfate, iron oxide, iron fumarate, iron lactate, iron oxalate, iron sulfide, tin acetate, tin chloride, tin diphosphate, tin oxalate, tin oxide, sulfuric acid Low atomic valence metal salts such as tin; such as ethylene glycol, glycerol, formaldehyde, hydroquinone, gallic phenol, tannins, tannic acid, salicylic acid, D-glucose and other sugars, as long as they are soluble in the dispersion medium and reducing the metal salt is not particularly limited. Where the reducing agent is used, light and/or heat may be applied to promote the reduction reaction.
作為使用所述金屬鹽、「具有極性基的胺」、分散溶媒及還原劑來製備由「具有極性基的胺」被覆的金屬粒子的具體方法,例如可列舉如下方法等:將所述金屬鹽溶解於有機溶媒(例如甲苯等)中製備金屬鹽溶液,於該金屬鹽溶液中添加作為分散劑的有機物,繼而向其中緩慢滴加溶解有還原劑的溶液。As a specific method for producing metal particles coated with the "amine having a polar group" using the metal salt, the "amine having a polar group", a dispersion solvent, and a reducing agent, for example, the following method is mentioned: A metal salt solution is prepared by dissolving in an organic solvent (for example, toluene, etc.), an organic substance as a dispersant is added to the metal salt solution, and the solution in which the reducing agent is dissolved is gradually added dropwise thereto.
於以所述方式獲得的包含由「具有極性基的胺」被覆的金屬粒子的分散液中,除存在金屬粒子以外,亦存在金屬鹽的抗衡離子、還原劑的殘留物或分散劑,存在液體整體的電解質濃度或有機物濃度高的傾向。此種狀態的液體的導電度高,因此引起金屬粒子的凝結,容易沈澱。或者,即便不沈澱,若殘留金屬鹽的抗衡離子、還原劑的殘留物、或分散所需的量以上的過量的分散劑,則有導電性惡化的擔憂。因此,藉由對包含所述金屬粒子的溶液進行清洗並除去多餘的殘留物,可確實地獲得由有機物被覆的金屬粒子。In the dispersion liquid containing the metal particles coated with the "amine having a polar group" obtained in the manner described above, in addition to the metal particles, the counterion of the metal salt, the residue of the reducing agent, or the dispersant are also present, and the liquid is present. The overall electrolyte concentration or organic matter concentration tends to be high. The liquid in this state has high electrical conductivity, and thus causes coagulation of the metal particles, which tends to precipitate. Or even if it does not precipitate, if the counterion of a metal salt, the residue of a reducing agent, or the excess dispersing agent of the quantity required for dispersion|distribution remains, there exists a possibility that electroconductivity may deteriorate. Therefore, by washing the solution containing the metal particles and removing excess residues, metal particles coated with organic substances can be surely obtained.
作為所述清洗方法,例如可列舉:重覆幾次如下步驟的方法,所述步驟是將包含由「具有極性基的胺」被覆的金屬粒子的分散液靜置一定時間,除去產生的上清液後,加入醇(甲醇等)再次攪拌,進而靜置一定時間並除去產生的上清液;代替所述靜置而進行離心分離的方法;利用超濾裝置或離子交換裝置等進行脫鹽的方法等。藉由利用此種清洗來除去多餘的殘留物並且去除有機溶媒,可獲得供於本實施形態的由「具有極性基的胺」被覆的金屬粒子。Examples of the cleaning method include, for example, a method of repeating several times the step of leaving a dispersion liquid containing metal particles coated with an "amine having a polar group" for a certain period of time, and removing the generated supernatant After the liquid, add alcohol (methanol, etc.) and stir again, and then let stand for a certain period of time and remove the supernatant; instead of the standstill, the method of centrifugal separation; the method of desalination by using an ultrafiltration device or an ion exchange device Wait. By removing the excess residue and removing the organic solvent by such washing, metal particles coated with the "amine having a polar group" used in the present embodiment can be obtained.
本實施形態的接合用組成物藉由將所述中獲得的由「具有極性基的胺」被覆的金屬粒子與所述本實施形態中說明的分散介質(包含二醇,25℃下的黏度為100 mPa・s~300 mPa・s)加以混合來獲得。由該「具有極性基的胺」被覆的金屬粒子與所述分散介質的混合方法並無特別限定,可使用攪拌機或攪拌器等並利用先前公知的方法來進行。可利用刮刀(spatula)之類的物品進行攪拌,選擇適當輸出的超音波均質機。The bonding composition of the present embodiment is obtained by mixing the metal particles coated with the "amine having a polar group" obtained in the above and the dispersion medium described in the present embodiment (including diol, and the viscosity at 25°C is 100 mPa・s~300 mPa・s) and mixed to obtain. The mixing method of the metal particles coated with the "amine having a polar group" and the dispersion medium is not particularly limited, and can be performed by a conventionally known method using a stirrer, a stirrer, or the like. It can be stirred with a spatula or the like, and an ultrasonic homogenizer with an appropriate output can be selected.
再者,於獲得包含多種金屬的金屬膠體分散液的情況下,作為其製造方法,並無特別限定,例如於製造包含銀與其他金屬的金屬膠體分散液的情況下,於所述由有機物(具有極性基的胺)被覆的金屬粒子的製備中,可分別製造包含金屬粒子的分散液與包含其他金屬粒子的分散液,之後進行混合,亦可將銀離子溶液與其他金屬離子溶液混合,之後進行還原。Furthermore, in the case of obtaining a metal colloid dispersion liquid containing multiple metals, the production method thereof is not particularly limited. For example, in the case of producing a metal colloid dispersion liquid containing silver and other metals, the organic In the preparation of metal particles coated with amines with polar groups, a dispersion liquid containing metal particles and a dispersion liquid containing other metal particles can be produced separately, and then mixed, or the silver ion solution can also be mixed with other metal ion solutions, and then to restore.
於使用所述金屬胺錯合物法的情況下,例如只要藉由第一步驟與第二步驟來製造金屬粒子即可,所述第一步驟是將包含具有極性基的胺的胺液與包含金屬原子的金屬化合物混合,生成包含該金屬化合物與胺的錯化合物,所述第二步驟是藉由對該錯化合物進行加熱而分解來生成金屬粒子。In the case of using the metal amine complex method, for example, metal particles may be produced by the first step and the second step. The first step is to mix the amine solution containing the amine having a polar group with A metal compound of a metal atom is mixed to generate a zirconium compound containing the metal compound and an amine, and the second step is to generate metal particles by decomposing the zirconium compound by heating.
例如,於具有極性基的胺的存在下對由包含銀的草酸銀等金屬化合物與具有極性基的胺生成的錯化合物進行加熱,將該錯合物中包含的草酸根離子等金屬化合物分解並使生成的原子狀的銀凝聚,藉此可製造被具有極性基的胺的保護膜保護的銀粒子。For example, by heating an zirconium compound formed from a metal compound such as silver oxalate containing silver and an amine having a polar group in the presence of an amine having a polar group, the metal compound such as oxalate ion contained in the complex is decomposed and Aggregation of the generated atomic silver enables production of silver particles protected by a protective film of an amine having a polar group.
如此,於藉由在具有極性基的胺的存在下對金屬化合物的錯化合物進行熱分解來製造由具有極性基的胺被覆的金屬粒子的金屬胺錯合物分解法中,利用為單一種類的分子的金屬胺錯合物的分解反應而生成原子狀金屬,因此可於反應系統內均勻地生成原子狀金屬,與利用多種成分間的反應來生成金屬原子的情況相比較,構成反應的成分的組成波動引起的反應的不均勻得到抑制,特別是於以工業規模製造大量的金屬粉末時有利。As described above, in the metal amine complex decomposition method for producing metal particles coated with an amine having a polar group by thermally decomposing an zirconium compound of a metal compound in the presence of an amine having a polar group, a single type of metal amine complex is used. The atomic metal is generated by the decomposition reaction of the molecular metal amine complex, so atomic metal can be uniformly generated in the reaction system. Compared with the case where the metal atom is generated by the reaction between multiple components, the number of components constituting the reaction is higher. The inhomogeneity of the reaction caused by the fluctuation of the composition is suppressed, which is especially advantageous when producing a large amount of metal powder on an industrial scale.
另外,推測於金屬胺錯合物分解法中,具有極性基的胺分子與生成的金屬原子配位鍵結,藉由配位於該金屬原子上的具有極性基的胺分子的作用,產生凝聚時的金屬原子的運動得到控制。結果,可根據金屬胺錯合物分解法來製造非常微細、且粒度分佈窄的金屬粒子。In addition, in the metal amine complex decomposition method, it is presumed that the amine molecule having a polar group is coordinately bonded to the generated metal atom, and the aggregation occurs due to the action of the amine molecule having a polar group coordinated to the metal atom. The motion of the metal atoms is controlled. As a result, very fine metal particles having a narrow particle size distribution can be produced by the metal amine complex decomposition method.
進而,於所製造的金屬微粒子的表面,大量的具有極性基的胺分子亦產生比較弱的力的配位鍵結,該些於金屬粒子的表面形成緻密的保護被膜,因此可製造保存穩定性優異、表面潔淨的被覆金屬粒子。另外,形成該被膜的具有極性基的胺中,烷氧基胺分子可藉由加熱等而容易地脫離,因此可製造可於比較低的溫度(200℃以下)下進行燒結的金屬粒子。Furthermore, a large number of amine molecules having polar groups also generate relatively weak coordination bonds on the surface of the metal particles to be produced, and these form a dense protective film on the surface of the metal particles, so that storage stability can be produced. Excellent, clean surface coated metal particles. In addition, in the amine having a polar group forming the film, alkoxyamine molecules can be easily removed by heating or the like, so that metal particles that can be sintered at a relatively low temperature (200° C. or lower) can be produced.
含有以上般獲得的由具有極性基的胺被覆的金屬粒子的本實施形態的接合用組成物可防止金屬粒子與分散介質(包含二醇,25℃下的黏度為100 mPa・s~300 mPa・s)的分離,可於無損塗佈穩定性的範圍內添加各種無機成分或有機成分。The bonding composition of the present embodiment containing the metal particles obtained as described above and coated with an amine having a polar group can prevent the metal particles and the dispersion medium (including diol, the viscosity at 25°C being 100 mPa・s to 300 mPa・ s), and various inorganic or organic components can be added within the range that does not impair coating stability.
再者,於製備由與「具有極性基的胺」不同的有機保護成分被覆表面的第二金屬粒子的情況下,於所述說明中的由「具有極性基的胺」被覆的金屬粒子(金屬膠體粒子)的製備方法中,代替「具有極性基的胺」而使用所期望的有機保護成分,藉此可製備與第一金屬粒子不同的由有機保護成分被覆表面的第二金屬粒子。Furthermore, in the case of preparing the second metal particle whose surface is covered with an organic protective component different from the "amine having a polar group", the metal particle (metal particle) covered with the "amine having a polar group" in the description In the production method of colloidal particles), a desired organic protective component is used instead of the "amine having a polar group", whereby the second metal particle whose surface is coated with an organic protective component different from the first metal particle can be prepared.
(接合方法) 若使用本實施形態的接合用組成物,則於伴隨加熱的構件彼此的接合中可獲得高的接合強度。即,藉由將所述接合用組成物塗佈於第一被接合構件與第二被接合構件之間的接合用組成物塗佈步驟、以及對塗佈於第一被接合構件與第二被接合構件之間的接合用組成物於所期望的溫度(例如,200℃以下、較佳為150℃左右)下進行煆燒並加以接合的接合步驟,可將第一被接合構件與第二被接合構件接合。(joining method) When the composition for bonding of the present embodiment is used, high bonding strength can be obtained in bonding of members with heating. That is, by applying the bonding composition to the bonding composition between the first bonded member and the second bonded member, and applying the bonding composition to the first bonded member and the second bonded member. The bonding step in which the bonding composition between the bonding members is fired at a desired temperature (for example, 200° C. or lower, preferably about 150° C.) and bonding is performed, and the first member to be bonded and the second member to be bonded can be joined together. The engaging member engages.
於該接合步驟時,亦可將第一被接合構件與第二被接合構件向相向的方向加壓,但即便不特別加壓亦可獲得充分的接合強度亦為本發明的優點之一。另外,於進行煆燒時亦可階段性提高或降低溫度。另外,亦可預先於被接合構件的表面上塗佈界面活性劑或表面活化劑等。In this joining step, the first joined member and the second joined member may be pressurized in opposite directions, but it is one of the advantages of the present invention that sufficient joining strength can be obtained even without special pressurization. In addition, the temperature may be raised or lowered stepwise during the sintering. Moreover, a surfactant, a surfactant, etc. may be apply|coated to the surface of a to-be-joined member in advance.
本發明者反覆努力研究,結果發現,若使用所述本實施形態的接合用組成物作為所述接合用組成物塗佈步驟中的接合用組成物,則可防止接合用組成物中分散介質與金屬粒子的分離,塗佈穩定性高,可以高的接合強度更可靠地接合第一被接合構件與第二被接合構件(可獲得接合體)。The inventors of the present invention have repeatedly studied and found that, when the bonding composition of the present embodiment is used as the bonding composition in the bonding composition coating step, the dispersion medium in the bonding composition can be prevented from interacting with the bonding composition. The separation of the metal particles has high coating stability, and the first member to be joined and the second member to be joined can be joined more reliably with high joining strength (a joined body can be obtained).
此處,所謂本實施形態的接合用組成物的「塗佈」,是既包含將接合用組成物塗佈為面狀的情況亦包含塗佈(描繪)為線狀的情況的概念。包含進行塗佈並藉由加熱而煆燒前的狀態的接合用組成物的塗膜的形狀可設為所期望的形狀。因此,於藉由加熱進行煆燒後的本實施形態的接合體中,接合用組成物是均包含面狀的接合層及線狀的接合層的概念,該些面狀的接合層及線狀的接合層可連續亦可不連續,可包含連續的部分與不連續的部分。Here, "application" of the bonding composition of the present embodiment is a concept that includes both the case where the bonding composition is applied in a planar shape and the case where the bonding composition is applied (drawn) in a linear shape. The shape of the coating film containing the composition for bonding in the state before being coated and baked by heating can be set as a desired shape. Therefore, in the joined body of the present embodiment after sintering by heating, the composition for joining is a concept including a planar joining layer and a linear joining layer, and these planar joining layers and linear joining layers The bonding layer can be continuous or discontinuous, and can include continuous parts and discontinuous parts.
作為可於本實施形態中使用的第一被接合構件及第二被接合構件,只要為可塗佈接合用組成物並藉由加熱進行煆燒而接合的構件即可,並無特別限制,較佳為具備不會因接合時的溫度而損傷的程度的耐熱性的構件。The first member to be joined and the second member to be joined that can be used in the present embodiment are not particularly limited as long as they are members that can be joined by applying a joining composition and sintering them by heating. Preferably, it is a member having heat resistance to such an extent that it is not damaged by the temperature at the time of joining.
作為構成此種被接合構件的材料,例如可列舉:聚醯胺(polyamide,PA)、聚醯亞胺(polyimide,PI)、聚醯胺醯亞胺(polyamide imide,PAI)、聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)、聚對苯二甲酸丁二酯(polybutylene terephthalate,PBT)、聚萘二甲酸乙二酯(polyethylene naphthalate,PEN)等聚酯、聚碳酸酯(polycarbonate,PC)、聚醚碸(polyether sulfone,PES)、乙烯基樹脂、氟樹脂、液晶聚合物、陶瓷、玻璃或金屬等,其中較佳為金屬製的被接合構件。較佳為金屬製的被接合構件是因為耐熱性優異,並且與無機粒子為金屬的本發明的金屬接合用組成物的親和性優異。Examples of materials constituting such a member to be joined include polyamide (PA), polyimide (PI), polyamide imide (PAI), and polyterephthalene. Polyester (polyethylene terephthalate, PET), polybutylene terephthalate (PBT), polyethylene naphthalate (polyethylene naphthalate, PEN) and other polyesters, polycarbonate (polycarbonate, PC) ), polyether sulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramic, glass, metal, etc., among them, a metal-made member to be joined is preferable. A metal-made member to be joined is preferable because it is excellent in heat resistance and has excellent affinity with the composition for metal joining of the present invention in which the inorganic particles are metal.
另外,被接合構件例如可為板狀或帶(strip)狀等各種形狀,可為剛性(rigid)亦可為柔性(flexible)。亦可適宜選擇基材的厚度。為了提高接著性或密接性或者其他目的,亦可使用形成有表面層的構件或實施有親水化處理等表面處理的構件。Moreover, the to-be-joined member may be various shapes, such as a plate shape and a strip shape, for example, and may be rigid (rigid) or flexible (flexible). The thickness of the base material can also be appropriately selected. In order to improve adhesiveness, adhesiveness, or other purposes, a member having a surface layer formed thereon or a member having a surface treatment such as a hydrophilization treatment can also be used.
作為所述第一被接合構件及第二被接合構件,可列舉:樹脂基板、金屬板、LED等發光元件、半導體晶片、形成有電子電路的陶瓷基板等。本實施形態的接合用組成物由於所獲得的燒結體的接合強度高,因此亦可於LED等發光元件、半導體晶片等、與金屬基板、陶瓷基板等的接合中較佳地使用。Examples of the first member to be joined and the second member to be joined include resin substrates, metal plates, light-emitting elements such as LEDs, semiconductor wafers, ceramic substrates on which electronic circuits are formed, and the like. Since the obtained sintered body has a high bonding strength, the bonding composition of the present embodiment can also be suitably used for bonding of light-emitting elements such as LEDs, semiconductor wafers, and the like to metal substrates, ceramic substrates, and the like.
作為將接合用組成物塗佈於所述第一被接合構件及第二被接合構件上的步驟,可使用各種方法,例如可使用:浸漬、網版印刷、噴霧式、棒塗式、旋塗式、噴墨式、分配器式、針轉印(pin transfer)法、壓模(stamping)法、利用毛刷的塗佈方式、流延式、柔版式、凹版式、平板法、轉印法、親水疏水圖案法、注射器式、針轉印、模版印刷等。其中,本實施形態的接合用組成物由於固體成分濃度高,因此可於分配器式、針轉印、模版印刷中較佳地使用。As the step of applying the composition for bonding on the first and second members to be joined, various methods can be used, for example, dipping, screen printing, spraying, bar coating, spin coating can be used type, inkjet type, dispenser type, pin transfer method, stamping method, coating method with brush, casting type, flexo type, gravure type, flat plate method, transfer method , Hydrophilic and hydrophobic pattern method, syringe type, needle transfer, stencil printing, etc. Among them, the bonding composition of the present embodiment can be preferably used in dispenser type, needle transfer, and stencil printing because of its high solid content concentration.
藉由在不會損傷被接合構件的範圍內,將如所述般塗佈後的塗膜加熱至例如200℃以下的溫度而進行煆燒,從而可獲得本實施形態的接合體。於本實施形態中,如之前敘述般,由於使用本實施形態的接合用組成物,因此塗佈穩定性高,可獲得相對於被接合構件具有優異的密接性的接合層,可更可靠地獲得強的接合強度。The joined body of the present embodiment can be obtained by heating the coating film applied as described above to, for example, a temperature of 200° C. or lower within a range that does not damage the member to be joined. In this embodiment, as described above, since the bonding composition of this embodiment is used, the coating stability is high, and a bonding layer having excellent adhesiveness with respect to the member to be bonded can be obtained, which can be obtained more reliably. Strong bonding strength.
於本實施形態中,在接合用組成物包含黏合劑成分的情況下,就提高接合層的強度及提高被接合構件間的接合強度等觀點而言,黏合劑成分亦進行燒結,但根據情況,為了適用於各種印刷法而將調整接合用組成物的黏度作為黏合劑成分的主要目的,可控制煆燒條件而將黏合劑成分全部去除。In the present embodiment, when the bonding composition contains a binder component, the binder component is also sintered from the viewpoints of enhancing the strength of the bonding layer and improving the bonding strength between the members to be joined. In order to apply to various printing methods, the main purpose of adjusting the viscosity of the bonding composition as an adhesive component is to control the sintering conditions and remove all the adhesive components.
進行所述煆燒的方法並無特別限定,例如可使用先前公知的烘箱等以塗佈或描繪於被接合構件上的所述接合用組成物的溫度為例如200℃以下的方式進行煆燒,藉此進行接合。所述煆燒的溫度的下限未必受到限定,較佳為可將被接合構件彼此接合的溫度,且為無損本發明的效果的範圍的溫度。此處,於所述煆燒後的接合用組成物中,就獲得盡可能高的接合強度的方面而言,有機物的殘存量越少越佳,但於無損本發明的效果的範圍內,有機物的一部分亦可殘存。The method for performing the sintering is not particularly limited. For example, the sintering can be performed so that the temperature of the bonding composition applied or drawn on the member to be joined is, for example, 200° C. or lower using a conventionally known oven or the like. This is used to join. The lower limit of the sintering temperature is not necessarily limited, but is preferably a temperature at which the members to be joined can be joined to each other, and is a temperature within a range that does not impair the effects of the present invention. Here, in the composition for bonding after the calcination, in terms of obtaining the highest possible bonding strength, it is preferable that the residual amount of the organic matter is as small as possible. part of it also survives.
再者,本發明的接合用組成物中包含有機物,但與先前的例如利用環氧樹脂等的熱硬化者不同,並非藉由有機物的作用來獲得煆燒後的接合強度,而如所述般藉由熔接的金屬粒子的熔接來獲得充分的接合強度。因此,即便於在接合後置於溫度較接合溫度高的使用環境中而殘存的有機物不劣化而分解及/或消失的情況下,亦無接合強度降低的擔憂,因此耐熱性優異。Furthermore, the bonding composition of the present invention contains an organic substance, but unlike the conventional thermosetting epoxy resin, for example, the bonding strength after firing is not obtained by the action of the organic substance, but as described above. Sufficient bonding strength is obtained by welding of the welded metal particles. Therefore, even if the remaining organic matter is decomposed and/or disappears without deteriorating after joining in a use environment with a temperature higher than the joining temperature, there is no fear of a decrease in the joining strength, and thus it is excellent in heat resistance.
根據本實施形態的接合用組成物,可實現具有即便藉由例如200℃以下的低溫加熱進行煆燒亦可表現出高的導電性的接合層的接合,因此可將比較不耐熱的被接合構件彼此接合。另外,煆燒時間並無特別限定,只要為可根據煆燒溫度進行接合的煆燒時間即可。According to the bonding composition of the present embodiment, bonding having a bonding layer that exhibits high electrical conductivity even when sintered by heating at a low temperature of, for example, 200° C. or lower can be realized, so that the members to be bonded which are relatively unstable to heat can be bonded. joined to each other. In addition, the sintering time is not particularly limited, as long as it is a sintering time that can be joined according to the sintering temperature.
於本實施形態中,為了進一步提高所述被接合構件與接合層的密接性,亦可進行所述被接合構件的表面處理。作為所述表面處理方法,例如可列舉:進行電暈處理、電漿處理、紫外線(ultraviolet,UV)處理、電子束處理等乾式處理的方法、於基材上預先設置底塗層或導電性糊接收層的方法等。In this embodiment, in order to further improve the adhesiveness of the said to-be-joined member and a bonding layer, the surface treatment of the said to-be-joined member may be performed. As the surface treatment method, for example, a method of performing dry treatment such as corona treatment, plasma treatment, ultraviolet (ultraviolet, UV) treatment, and electron beam treatment, and preliminarily providing a primer layer or conductive paste on a base material can be mentioned. methods of the receiving layer, etc.
以上,對本發明的代表性實施形態進行了說明,但本發明並不僅由該些內容限定。例如於所述實施形態中,對採用金屬粒子作為無機粒子的金屬膠體分散液進行了說明,亦可使用例如導電性、導熱性、介電性、離子傳導性等優異的摻錫氧化銦、氧化鋁、鈦酸鋇、磷酸鐵鋰等無機粒子。As mentioned above, although typical embodiment of this invention was described, this invention is not limited only by these contents. For example, in the above-described embodiment, the metal colloid dispersion liquid using metal particles as inorganic particles has been described. Inorganic particles such as aluminum, barium titanate, and lithium iron phosphate.
以下,揭示實施例對本發明更詳細地進行說明,但本發明並不僅由該些實施例限定。Hereinafter, the present invention will be described in more detail by showing examples, but the present invention is not limited only by these examples.
<第一金屬粒子> (1-1)金屬微粒子A1 將3-乙氧基丙基胺(富士軟片和光純藥(股)製造的試劑特級,沸點132℃)11.0 g與3-甲氧基丙基胺(富士軟片和光純藥(股)製造的試劑一級,沸點120℃)7.0 g混合,並利用磁攪拌器充分進行攪拌。一邊進行攪拌一邊向其中添加草酸銀10.0 g,使其增稠。將所獲得的黏性物質放入至120℃的恆溫槽中,反應約15分鐘而獲得反應產物。向所述反應產物中加入甲醇10 ml並進行攪拌後,利用離心分離使銀微粒子沈澱並加以分離,捨棄上清液。將所述操作再重覆一次而獲得6 g的金屬微粒子A1。 使用利用SEM(日立股份有限公司製造的S-4800型)拍攝的粒子圖像,算出所獲得的金屬微粒子A1的數量平均一次粒徑(算術平均一次粒徑)。算術平均一次粒徑是根據於不同的拍攝點獲得的5點以上的圖像對合計200個以上的粒子使用圖像處理軟體(三谷公司(MITANI CORPORATION),WinROOF)進行算出。金屬微粒子A1的算術平均一次粒徑為50 nm,標準偏差為14.2 nm。利用下述式(1)獲得的變異係數為28.4%。 變異係數(%)=一次粒徑的標準偏差/平均一次粒徑×100 (1)<First Metal Particles> (1-1) Metal fine particle A1 11.0 g of 3-ethoxypropylamine (reagents manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., boiling point 132°C) 11.0 g and 3-methoxypropylamine (reagents manufactured by Fujifilm Wako Pure Chemical Industries Ltd.) Grade 1, boiling point 120°C) 7.0 g was mixed and stirred well with a magnetic stirrer. To this was added 10.0 g of silver oxalate while stirring to thicken. The obtained viscous substance was put into a thermostatic bath at 120° C. and reacted for about 15 minutes to obtain a reaction product. After adding 10 ml of methanol to the reaction product and stirring, the silver fine particles were precipitated and separated by centrifugation, and the supernatant was discarded. The operation was repeated once more to obtain 6 g of metal fine particles A1. The number-average primary particle size (arithmetic average primary particle size) of the obtained metal fine particles A1 was calculated using a particle image captured by SEM (S-4800, manufactured by Hitachi, Ltd.). The arithmetic mean primary particle size was calculated using an image processing software (MITANI CORPORATION, WinROOF) for a total of 200 or more particles from five or more images obtained at different imaging points. The arithmetic mean primary particle diameter of the metal microparticles A1 was 50 nm, and the standard deviation was 14.2 nm. The coefficient of variation obtained by the following formula (1) was 28.4%. Coefficient of variation (%) = standard deviation of primary particle size/average primary particle size × 100 (1)
(1-2)金屬微粒子A2 代替3-乙氧基丙基胺11.0 g與3-甲氧基丙基胺7.0 g而添加己基胺25.0 g(富士軟片和光純藥(股)製造的試劑一級,沸點130℃),除此以外與金屬微粒子A1的製法同樣地製作金屬微粒子A2。金屬微粒子A2的算術平均一次粒徑為59 nm,標準偏差為15.4 nm,變異係數為35.0%。(1-2) Metal fine particles A2 In place of 11.0 g of 3-ethoxypropylamine and 7.0 g of 3-methoxypropylamine, 25.0 g of hexylamine (reagent grade 1 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., boiling point 130°C) was added, except that The metal fine particles A2 were produced in the same manner as the production method of the metal fine particles A1. The arithmetic mean primary particle size of the metal microparticles A2 was 59 nm, the standard deviation was 15.4 nm, and the coefficient of variation was 35.0%.
<第二金屬粒子> (2-1)金屬微粒子B1 代替3-乙氧基丙基胺11.0 g與3-甲氧基丙基胺7.0 g而添加3-乙氧基丙基胺10.0 g與2-(2-胺基乙氧基)乙醇(富士軟片和光純藥(股)製造的試劑一級,沸點220℃)20.0 g,除此以外與金屬微粒子A1的製法同樣地製作金屬微粒子B1。金屬微粒子B1的算術平均一次粒徑為300 nm,標準偏差為180 nm,變異係數為60.0%。<Second Metal Particles> (2-1) Metal fine particle B1 Instead of 11.0 g of 3-ethoxypropylamine and 7.0 g of 3-methoxypropylamine, 10.0 g of 3-ethoxypropylamine and 2-(2-aminoethoxy)ethanol (Fuji Films) were added. Metal fine particles B1 were produced in the same manner as the production method of metal fine particles A1, except that the reagent grade 1 manufactured by Wako Pure Chemical Industries, Ltd., boiling point 220°C) was 20.0 g. The arithmetic mean primary particle size of the metal microparticle B1 was 300 nm, the standard deviation was 180 nm, and the coefficient of variation was 60.0%.
<接合用組成物> (實施例1) 將2 g的作為第一金屬粒子的金屬微粒子A1、4.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.11 g及2,4-二乙基-1,5-戊二醇0.16 g、0.018 g的作為高分子分散劑的索努帕斯16000,並加以攪拌脫泡,藉此製作實施例1的接合用組成物。<Joint composition> (Example 1) 2 g of the metal fine particles A1 as the first metal particles and 4.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.11 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. , 0.16 g of 5-pentanediol and 0.018 g of Sonopas 16000 as a polymer dispersant were stirred and defoamed to prepare the bonding composition of Example 1.
(實施例2) 加入作為分散介質的異十三烷醇0.15 g及2,4-二乙基-1,5-戊二醇0.23 g、0.025 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作實施例2的接合用組成物。(Example 2) 0.15 g of isotridecanol as a dispersion medium, 0.23 g of 2,4-diethyl-1,5-pentanediol, and 0.025 g of Sonopas 16000 as a polymer dispersant were added. The bonding composition of Example 2 was produced in the same manner as in Example 1.
(實施例3) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.09 g及2,4-二乙基-1,5-戊二醇0.07 g、2-乙基-1,3-己二醇0.07 g、0.015 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作實施例3的接合用組成物。(Example 3) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.09 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. , 0.07 g of 5-pentanediol, 0.07 g of 2-ethyl-1,3-hexanediol, and 0.015 g of Sonopas 16000 as a polymer dispersant were prepared in the same manner as in Example 1. The bonding composition of Example 3.
(實施例4) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.07 g及2,4-二乙基-1,5-戊二醇0.07 g、2-乙基-1,3-己二醇0.09 g、0.015 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作實施例4的接合用組成物。(Example 4) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.07 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. , 0.07 g of 5-pentanediol, 0.09 g of 2-ethyl-1,3-hexanediol, and 0.015 g of Sonopas 16000 as a polymer dispersant were prepared in the same manner as in Example 1. The bonding composition of Example 4.
(實施例5) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.04 g及2,4-二乙基-1,5-戊二醇0.07 g、2-乙基-1,3-己二醇0.11 g、0.015 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作實施例5的接合用組成物。(Example 5) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.04 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. , 0.07 g of 5-pentanediol, 0.11 g of 2-ethyl-1,3-hexanediol, and 0.015 g of Sonopas 16000 as a polymer dispersant were prepared in the same manner as in Example 1. The bonding composition of Example 5.
(實施例6) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的2-乙基-1,3-己二醇0.14 g及3-甲基-1,3-丁二醇0.14 g、0.019 g的作為高分子分散劑的迪斯帕畢克-118,除此以外與實施例1同樣地製作實施例6的接合用組成物。(Example 6) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.14 g of 2-ethyl-1,3-hexanediol and 3- The bonding composition of Example 6 was prepared in the same manner as in Example 1, except that 0.14 g of methyl-1,3-butanediol and 0.019 g of Dispersive-118 as a polymer dispersant were used.
(實施例7) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的2-乙基-1,3-己二醇0.08 g及3-甲基-1,3-丁二醇0.20 g、0.023 g的作為高分子分散劑的迪斯帕畢克-190,除此以外與實施例1同樣地製作實施例7的接合用組成物。(Example 7) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.08 g of 2-ethyl-1,3-hexanediol and 3- The bonding composition of Example 7 was produced in the same manner as in Example 1, except that 0.20 g of methyl-1,3-butanediol and 0.023 g of Dispersive-190 as a polymer dispersant were used.
(實施例8) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的3-甲基-1,3-丁二醇0.33 g、0.022 g的作為高分子分散劑的迪斯帕畢克-190,除此以外與實施例1同樣地製作實施例8的接合用組成物。(Example 8) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.33 g and 0.022 g of 3-methyl-1,3-butanediol were added as the dispersion medium. The bonding composition of Example 8 was prepared in the same manner as in Example 1, except that the polymer dispersant was DISPERBIC-190.
(實施例9) 將2 g的作為第一金屬粒子的金屬微粒子A1、2 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的2-乙基-1,3-己二醇0.28 g、0.017 g的作為高分子分散劑的迪斯帕畢克-118,除此以外與實施例1同樣地製作實施例9的接合用組成物。(Example 9) 2 g of the metal fine particles A1 as the first metal particles and 2 g of the metal fine particles B1 as the second metal particles were mixed, and 0.28 g and 0.017 g of 2-ethyl-1,3-hexanediol were added as the dispersion medium. The composition for bonding of Example 9 was produced in the same manner as in Example 1, except that the polymer dispersant was Dispersive-118.
(比較例1) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.20 g、0.013 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作比較例1的接合用組成物。(Comparative Example 1) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.20 g of isotridecanol and 0.013 g of Isotridecanol as a dispersion medium were added as a polymer dispersant. The bonding composition of Comparative Example 1 was produced in the same manner as in Example 1 except that Sonupas 16000 was used.
(比較例2) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.14 g及2,4-二乙基-1,5-戊二醇0.07 g、0.014 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作比較例2的接合用組成物。(Comparative Example 2) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.14 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. The bonding composition of Comparative Example 2 was prepared in the same manner as in Example 1, except that 0.07 g of 5-pentanediol and 0.014 g of Sonopas 16000 as a polymer dispersant were used.
(比較例3) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.19 g及2,4-二乙基-1,5-戊二醇0.05 g、0.016 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作比較例3的接合用組成物。(Comparative Example 3) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.19 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. The bonding composition of Comparative Example 3 was prepared in the same manner as in Example 1, except that 0.05 g of 5-pentanediol and 0.016 g of Sonopas 16000 as a polymer dispersant were used.
(比較例4) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.06 g及2,4-二乙基-1,5-戊二醇0.18 g、0.016 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作比較例4的接合用組成物。(Comparative Example 4) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.06 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. The bonding composition of Comparative Example 4 was prepared in the same manner as in Example 1, except that 0.18 g of 5-pentanediol and 0.016 g of Sonopas 16000 as a polymer dispersant were used.
(比較例5) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.04 g及2,4-二乙基-1,5-戊二醇0.18 g、0.015 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作比較例5的接合用組成物。(Comparative Example 5) 2 g of the metal fine particles A1 as the first metal particles and 2.1 g of the metal fine particles B1 as the second metal particles were mixed, and 0.04 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. The bonding composition of Comparative Example 5 was prepared in the same manner as in Example 1, except that 0.18 g of 5-pentanediol and 0.015 g of Sonopas 16000 as a polymer dispersant were used.
(比較例6) 將1 g的作為第一金屬粒子的金屬微粒子A1、4.3 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的異十三烷醇0.10 g及2,4-二乙基-1,5-戊二醇0.15 g、0.017 g的作為高分子分散劑的索努帕斯16000,除此以外與實施例1同樣地製作比較例6的接合用組成物。(Comparative Example 6) 1 g of the metal fine particles A1 as the first metal particles and 4.3 g of the metal fine particles B1 as the second metal particles were mixed, and 0.10 g of isotridecanol and 2,4-diethyl-1 were added as the dispersion medium. The bonding composition of Comparative Example 6 was prepared in the same manner as in Example 1, except that 0.15 g of 5-pentanediol and 0.017 g of Sonopas 16000 as a polymer dispersant were used.
(比較例7) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,添加作為分散介質的2,4-二乙基-1,5-戊二醇0.12 g、2-乙基-1,3-己二醇0.28 g,不添加高分子分散劑,除此以外與實施例1同樣地製作比較例7的接合用組成物。(Comparative Example 7) 2 g of metal fine particles A1 as first metal particles and 2.1 g of metal fine particles B1 as second metal particles were mixed, and 0.12 g of 2,4-diethyl-1,5-pentanediol was added as a dispersion medium and 0.28 g of 2-ethyl-1,3-hexanediol, except that a polymer dispersant was not added, the bonding composition of Comparative Example 7 was produced in the same manner as in Example 1.
(比較例8) 將2 g的作為第一金屬粒子的金屬微粒子A1、2.1 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的2-乙基-1,3-己二醇0.15 g、3-甲基-1,3-丁二醇0.15 g、0.22 g的作為高分子分散劑的迪斯帕畢克-118,除此以外與實施例1同樣地製作比較例8的接合用組成物。(Comparative Example 8) 2 g of metal fine particles A1 as first metal particles and 2.1 g of metal fine particles B1 as second metal particles were mixed, and 0.15 g of 2-ethyl-1,3-hexanediol, 3- A composition for bonding of Comparative Example 8 was prepared in the same manner as in Example 1, except that 0.15 g of methyl-1,3-butanediol and 0.22 g of Disparbic-118 as a polymer dispersant were used.
(比較例9) 將2 g的作為第一金屬粒子的金屬微粒子A2、2 g的作為第二金屬粒子的金屬微粒子B1混合,加入作為分散介質的2-乙基-1,3-己二醇0.14 g、3-甲基-1,3-丁二醇0.32 g、0.03 g的作為高分子分散劑的迪斯帕畢克-190,除此以外與實施例1同樣地製作比較例9的接合用組成物。(Comparative Example 9) 2 g of the metal fine particles A2 as the first metal particles and 2 g of the metal fine particles B1 as the second metal particles were mixed, and 0.14 g of 2-ethyl-1,3-hexanediol, 3- A bonding composition of Comparative Example 9 was prepared in the same manner as in Example 1, except that 0.32 g of methyl-1,3-butanediol and 0.03 g of Dispersive-190 as a polymer dispersant were used.
<評價> (1)重量減少率的測定 對於實施例及比較例的接合用組成物,使用差動型示差熱天平(理學(Rigaku)公司製造,TG8120)並利用熱重分析法來測定重量減少率。具體而言,於大氣環境下,對接合用組成物以10℃/min的升溫速度進行加熱,測定室溫(25℃)~550℃為止的重量減少率。利用以下的式(2)算出接合用組成物的固體成分濃度。 接合用組成物的固體成分濃度(重量%)=100-室溫~550℃為止的重量減少量(重量%) (2)<Evaluation> (1) Measurement of weight loss rate About the composition for bonding of an Example and a comparative example, the weight reduction rate was measured by the thermogravimetric analysis method using a differential type differential thermobalance (the Rigaku company make, TG8120). Specifically, the bonding composition was heated at a temperature increase rate of 10° C./min in an atmospheric environment, and the weight loss rate from room temperature (25° C.) to 550° C. was measured. The solid content concentration of the bonding composition was calculated by the following formula (2). Solid content concentration (% by weight) of the bonding composition = 100-Amount of weight loss (% by weight) from room temperature to 550°C (2)
(2)剪切黏度 對於實施例及比較例的接合用組成物,使用錐板型黏度計(安東帕(Anton Paar)公司製造的流變儀,MCR301)以如下測定條件測定剪切速度為10 s-1 時的剪切黏度(Pa·s)。 (測定條件) 測定模式:剪切模式 剪切速度:10 s-1 測定夾具:錐板CP-25-2 (直徑25 mm、角度2°、間隙0.105 mm) 測定溫度:25℃(2) Shear Viscosity For the bonding compositions of Examples and Comparative Examples, a shear rate of 10 was measured using a cone and plate viscometer (Rheometer, MCR301 manufactured by Anton Paar) under the following measurement conditions. Shear viscosity (Pa s) at s -1 . (Measurement conditions) Measurement mode: Shear mode Shear speed: 10 s -1 Measurement jig: Cone and plate CP-25-2 (diameter 25 mm, angle 2°, gap 0.105 mm) Measurement temperature: 25°C
(3)接合強度 於表面實施有金鍍敷的銅板(20 mm見方,厚度1 mm)的金鍍層上,使用裝片機(die bonder)(海索爾(hisol)公司製造)載置10 μg的接合用組成物,並於接合用組成物上積層帶金金屬化的藍寶石晶片(底面積:1000 μm×1000 μm,高度:200 μm),並且對於各實施例及比較例,製作積層有實施有金鍍敷的銅板、接合用組成物、以及帶金金屬化的藍寶石的積層體。 將所獲得的積層體放入至熱風循環式烘箱中,於大氣中歷時60分鐘自25℃升溫至200℃為止,並進行30分鐘煆燒。煆燒處理時,並不對積層體進行加壓。取出積層體後,於常溫下使用接合試驗機(力世科(rhesca)股份有限公司製造的接合試驗機(bonding tester)PTR1102)進行接合強度試驗。所述接合強度試驗中,將安裝於接合試驗機的加重感測器的寬度1.2 mm的工具(tool)配置於距所述銅板的表面為10.0 μm的高度處,以0.01 mm/sec使所述工具移動,並按壓利用所述接合用組成物進行接合的接合部分,測定自所述銅板剝離所述藍寶石時的加重,設為剝離時的接合強度。用剝離時的接合強度除以晶片的底面積,算出每單位面積的接合強度(MPa)。(3) Bonding strength On the gold plating layer of a copper plate (20 mm square, thickness 1 mm) on which gold plating was performed, 10 μg of the bonding composition was placed using a die bonder (manufactured by Hisol Corporation). , and a gold metallized sapphire wafer (bottom area: 1000 μm×1000 μm, height: 200 μm) was laminated on the bonding composition, and for each Example and Comparative A copper plate, a bonding composition, and a laminate of gold metallized sapphire. The obtained layered product was put into a hot air circulation oven, heated from 25°C to 200°C over 60 minutes in the air, and sintered for 30 minutes. During the sintering treatment, the laminate is not pressurized. After taking out the laminated body, a bonding strength test was performed at room temperature using a bonding tester (bonding tester PTR1102 manufactured by Rhesca Co., Ltd.). In the bonding strength test, a tool with a width of 1.2 mm attached to a weight sensor of a bonding testing machine was placed at a height of 10.0 μm from the surface of the copper plate, and the The tool was moved to press the joining portion joined by the joining composition, and the weight when the sapphire was peeled off from the copper plate was measured, and it was set as the joining strength at the time of peeling. The bonding strength per unit area (MPa) was calculated by dividing the bonding strength at the time of peeling by the bottom area of the wafer.
(4)連續塗佈穩定性 使用空氣脈衝式分配器(武藏高科技(Musashi Engineering)製造,S-SIGMA-CMV5)及機器人(武藏高科技製造,350PC Smart SM 300ΩX 350PCS-SM300MEGAX),按照1 mm間隔將填充至注射器中的實施例及比較例的接合用組成物於載玻片上塗佈2000處。噴嘴使用武藏高科技製造的TPND-27G-U(內徑0.2 mm),設為噴嘴/基板距離:0.2 mm,注射器溫度調節:25℃。 對塗佈後的點進行觀察,將可塗佈成半球狀者設為○,將可見塗佈不良(拉絲、或者溶劑與粒子分離)者設為×。(4) Continuous coating stability Using an air pulse type dispenser (manufactured by Musashi Engineering, S-SIGMA-CMV5) and a robot (manufactured by Musashi High-tech, 350PC Smart SM 300ΩX 350PCS-SM300MEGAX), filling into syringes at 1 mm intervals is performed The bonding compositions of Examples and Comparative Examples were applied to 2000 places on the glass slide. As the nozzle, TPND-27G-U (inner diameter: 0.2 mm) manufactured by Musashi High-Tech was used, and the nozzle/substrate distance was set to: 0.2 mm, and the temperature of the syringe was adjusted: 25°C. The dots after coating were observed, and those that could be coated in a hemispherical shape were set as ○, and those where coating defects (stretching, or separation of the solvent and particles) were seen were set as ×.
將實施例及比較例的接合用組成物的組成與評價結果彙總於下述表1中。The compositions and evaluation results of the bonding compositions of Examples and Comparative Examples are summarized in Table 1 below.
[表1]
實施例1~實施例9的接合用組成物均具有適度的接合強度,連續塗佈穩定性優異。 著眼於分散介質的黏度,對實施例1~實施例9、比較例1~比較例5進行比較時,分散介質的黏度處於特定的範圍(100 mPa・s~300 mPa・s)以外者即便包含二醇作為分散介質,金屬粒子與分散介質亦會發生分離,或者於塗佈時會發生拉絲等,無法良好地維持塗佈穩定性。 另外,確認比較例6時,雖然分散介質的黏度在特定的範圍內,但金屬粒子與分散介質發生分離,結果連續塗佈穩定性差。認為這是因為第一金屬粒子與第二金屬粒子的調配比超過了20:80~80:20。 另外,確認比較例7時,雖然分散介質的黏度在特定的範圍內,但金屬粒子與分散介質發生分離,結果連續塗佈穩定性差。認為這是因為不含有高分子分散劑。 另外,確認比較例8時,雖然分散介質的黏度在特定的範圍內,但金屬粒子與分散介質發生分離,結果連續塗佈穩定性差。認為這是因為比較例8的接合用組成物中的固體成分濃度未滿90重量%。 另外,確認比較例9時,雖然分散介質的黏度在特定的範圍內,但金屬粒子與分散介質發生分離,結果連續塗佈穩定性差。認為這是因為第一金屬粒子未由具有極性基的胺被覆。The bonding compositions of Examples 1 to 9 all had moderate bonding strengths and were excellent in continuous coating stability. Focusing on the viscosity of the dispersion medium, when comparing Examples 1 to 9 and Comparative Examples 1 to 5, the viscosity of the dispersion medium is outside the specified range (100 mPa・s to 300 mPa・s) even if it includes When diol is used as a dispersion medium, the metal particles and the dispersion medium may be separated, or stringing may occur during coating, and coating stability cannot be maintained well. In addition, in Comparative Example 6, although the viscosity of the dispersion medium was within a specific range, the metal particles were separated from the dispersion medium, resulting in poor continuous coating stability. This is considered to be because the blending ratio of the first metal particles and the second metal particles exceeded 20:80 to 80:20. In addition, in Comparative Example 7, although the viscosity of the dispersion medium was within a specific range, the metal particles were separated from the dispersion medium, resulting in poor continuous coating stability. It is considered that this is because a polymer dispersant is not contained. In addition, in Comparative Example 8, although the viscosity of the dispersion medium was within a specific range, the metal particles were separated from the dispersion medium, resulting in poor continuous coating stability. This is considered to be because the solid content concentration in the bonding composition of Comparative Example 8 was less than 90% by weight. In addition, in Comparative Example 9, although the viscosity of the dispersion medium was within a specific range, the metal particles were separated from the dispersion medium, resulting in poor continuous coating stability. It is considered that this is because the first metal particles are not coated with the amine having a polar group.
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